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  • Theoretical, Physical and Computational Chemistry  (1,576)
  • Turbulence
  • Wiley-Blackwell  (1,602)
  • American Meteorological Society  (41)
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  • 1
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2015. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 45 (2015): 2006–2024, doi:10.1175/JPO-D-14-0234.1.
    Description: The effects of wind-driven whitecapping on the evolution of the ocean surface boundary layer are examined using an idealized one-dimensional Reynolds-averaged Navier–Stokes numerical model. Whitecapping is parameterized as a flux of turbulent kinetic energy through the sea surface and through an adjustment of the turbulent length scale. Simulations begin with a two-layer configuration and use a wind that ramps to a steady stress. This study finds that the boundary layer begins to thicken sooner in simulations with whitecapping than without because whitecapping introduces energy to the base of the boundary layer sooner than shear production does. Even in the presence of whitecapping, shear production becomes important for several hours, but then inertial oscillations cause shear production and whitecapping to alternate as the dominant energy sources for mixing. Details of these results are sensitive to initial and forcing conditions, particularly to the turbulent length scale imposed by breaking waves and the transfer velocity of energy from waves to turbulence. After 1–2 days of steady wind, the boundary layer in whitecapping simulations has thickened more than the boundary layer in simulations without whitecapping by about 10%–50%, depending on the forcing and initial conditions.
    Description: We thank Skidmore College for financial and infrastructure support, and Skidmore and the National Science Foundation for funding travel to meetings where early versions of this work were presented. We also thank the National Science Foundation, Oregon State University, Jonathan Nash, and Joe Jurisa for funding and hosting a workshop on River Plume Mixing in October, 2013, where ideas and context for this paper were developed.
    Description: 2016-02-01
    Keywords: Circulation/ Dynamics ; Mixing ; Turbulence ; Wave breaking ; Wind stress ; Atm/Ocean Structure/ Phenomena ; Mixed layer
    Repository Name: Woods Hole Open Access Server
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  • 2
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2018. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 48 (2018): 1555-1566, doi:10.1175/JPO-D-17-0231.1.
    Description: A primary challenge in modeling flow over shallow coral reefs is accurately characterizing the bottom drag. Previous studies over continental shelves and sandy beaches suggest surface gravity waves should enhance the drag on the circulation over coral reefs. The influence of surface gravity waves on drag over four platform reefs in the Red Sea is examined using observations from 6-month deployments of current and pressure sensors burst sampling at 1Hz for 4–5min. Depth-average current fluctuations U0 within each burst are dominated by wave orbital velocities uw that account for 80%–90%of the burst variance and have a magnitude of order 10 cm s21, similar to the lower-frequency depth-average current Uavg. Previous studies have shown that the cross-reef bottom stress balances the pressure gradient over these reefs. A bottom stress estimate that neglects the waves (rCdaUavgjUavgj, where r is water density and Cda is a drag coefficient) balances the observed pressure gradient when uw is smaller than Uavg but underestimates the pressure gradient when uw is larger than Uavg (by a factor of 3–5 when uw 5 2Uavg), indicating the neglected waves enhance the bottom stress. In contrast, a bottom stress estimate that includes the waves [rCda(Uavg 1 U0)jUavg 1 U0j)] balances the observed pressure gradient independent of the relative size of uw and Uavg, indicating that this estimate accounts for the wave enhancement of the bottom stress. A parameterization proposed by Wright and Thompson provides a reasonable estimate of the total bottom stress (including the waves) given the burst-averaged current and the wave orbital velocity.
    Description: The Red Sea field program was supported by Awards USA 00002 and KSA 00011 made by KAUST. S. Lentz was supported for the analysis by NSF Award OCE-1558343.
    Description: 2019-01-13
    Keywords: Coastal flows ; Currents ; Dynamics ; Gravity waves ; Turbulence
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  • 3
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2009. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 39 (2009): 1077–1096, doi:10.1175/2008JPO4044.1.
    Description: Observations of turbulent kinetic energy (TKE) dynamics in the ocean surface boundary layer are presented here and compared with results from previous observational, numerical, and analytic studies. As in previous studies, the dissipation rate of TKE is found to be higher in the wavy ocean surface boundary layer than it would be in a flow past a rigid boundary with similar stress and buoyancy forcing. Estimates of the terms in the turbulent kinetic energy equation indicate that, unlike in a flow past a rigid boundary, the dissipation rates cannot be balanced by local production terms, suggesting that the transport of TKE is important in the ocean surface boundary layer. A simple analytic model containing parameterizations of production, dissipation, and transport reproduces key features of the vertical profile of TKE, including enhancement near the surface. The effective turbulent diffusion coefficient for heat is larger than would be expected in a rigid-boundary boundary layer. This diffusion coefficient is predicted reasonably well by a model that contains the effects of shear production, buoyancy forcing, and transport of TKE (thought to be related to wave breaking). Neglect of buoyancy forcing or wave breaking in the parameterization results in poor predictions of turbulent diffusivity. Langmuir turbulence was detected concurrently with a fraction of the turbulence quantities reported here, but these times did not stand out as having significant differences from observations when Langmuir turbulence was not detected.
    Description: The Office of Naval Research funded this work as a part of CBLAST-Low.
    Keywords: Turbulence ; Boundary layer ; Sea/ocean surface ; Air-sea interaction ; Energy transport
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  • 4
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2007. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 37 (2007): 1764-1777, doi:10.1175/jpo3098.1.
    Description: The vertical structure of the dissipation of turbulence kinetic energy was observed in the nearshore region (3.2-m mean water depth) with a tripod of three acoustic Doppler current meters off a sandy ocean beach. Surface and bottom boundary layer dissipation scaling concepts overlap in this region. No depth-limited wave breaking occurred at the tripod, but wind-induced whitecapping wave breaking did occur. Dissipation is maximum near the surface and minimum at middepth, with a secondary maximum near the bed. The observed dissipation does not follow a surfzone scaling, nor does it follow a “log layer” surface or bottom boundary layer scaling. At the upper two current meters, dissipation follows a modified deep-water breaking-wave scaling. Vertical shear in the mean currents is negligible and shear production magnitude is much less than dissipation, implying that the vertical diffusion of turbulence is important. The increased near-bed secondary dissipation maximum results from a decrease in the turbulent length scale.
    Description: Funding was provided by NSF and ONR.
    Keywords: Turbulence ; Kinetic energy ; Ocean
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  • 5
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2012. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 42 (2012): 2143–2152, doi:10.1175/JPO-D-12-027.1.
    Description: Direct measurements of turbulence levels in the Drake Passage region of the Southern Ocean show a marked enhancement over the Phoenix Ridge. At this site, the Antarctic Circumpolar Current (ACC) is constricted in its flow between the southern tip of South America and the northern tip of the Antarctic Peninsula. Observed turbulent kinetic energy dissipation rates are enhanced in the regions corresponding to the ACC frontal zones where strong flow reaches the bottom. In these areas, turbulent dissipation levels reach 10−8 W kg−1 at abyssal and middepths. The mixing enhancement in the frontal regions is sufficient to elevate the diapycnal turbulent diffusivity acting in the deep water above the axis of the ridge to 1 × 10−4 m2 s−1. This level is an order of magnitude larger than the mixing levels observed upstream in the ACC above smoother bathymetry. Outside of the frontal regions, dissipation rates are O(10−10) W kg−1, comparable to the background levels of turbulence found throughout most mid- and low-latitude regions of the global ocean.
    Description: This work was supported by the U.S. National Science Foundation and by the Natural Environment Research Council of the United Kingdom.
    Description: 2013-06-01
    Keywords: Southern Ocean ; Turbulence ; Diapycnal mixing
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  • 6
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2018. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 48 (2018): 435-453, doi:10.1175/JPO-D-17-0122.1.
    Description: Observations of surface waves, currents, and turbulence at the Columbia River mouth are used to investigate the source and vertical structure of turbulence in the surface boundary layer. Turbulent velocity data collected on board freely drifting Surface Wave Instrument Float with Tracking (SWIFT) buoys are corrected for platform motions to estimate turbulent kinetic energy (TKE) and TKE dissipation rates. Both of these quantities are correlated with wave steepness, which has previously been shown to determine wave breaking within the same dataset. Estimates of the turbulent length scale increase linearly with distance from the free surface, and roughness lengths estimated from velocity statistics scale with significant wave height. The vertical decay of turbulence is consistent with a balance between vertical diffusion and dissipation. Below a critical depth, a power-law scaling commonly applied in the literature works well to fit the data. Above this depth, an exponential scaling fits the data well. These results, which are in a surface-following reference frame, are reconciled with results from the literature in a fixed reference frame. A mapping between free-surface and mean-surface reference coordinates suggests 30% of the TKE is dissipated above the mean sea surface.
    Description: Funding for this project was provided by the Office of Naval Research as part of the RIVET-II DRI, and for the DARLA group.
    Keywords: Ocean ; Estuaries ; Gravity waves ; Turbulence ; Wave breaking ; In situ oceanic observations
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  • 7
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2007. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 37 (2007): 1496-1511, doi:10.1175/jpo3071.1.
    Description: Measurements collected in the York River estuary, Virginia, demonstrate the important impact that tidal and lateral asymmetries in turbulent mixing have on the tidally averaged residual circulation. A reduction in turbulent mixing during the ebb phase of the tide caused by tidal straining of the axial density gradient results in increased vertical velocity shear throughout the water column during the ebb tide. In the absence of significant lateral differences in turbulent mixing, the enhanced ebb-directed transport caused by tidal straining is balanced by a reduction in the net seaward-directed barotropic pressure gradient, resulting in laterally uniform two-layer residual flow. However, the channel–shoal morphology of many drowned river valley estuaries often leads to lateral gradients in turbulent mixing. Tidal straining may then lead to tidal asymmetries in turbulent mixing near the deeper channel while the neighboring shoals remain relatively well mixed. As a result, the largest lateral asymmetries in turbulent mixing occur at the end of the ebb tide when the channel is significantly more stratified than the shoals. The reduced friction at the end of ebb delays the onset of the flood tide, increasing the duration of ebb in the channel. Conversely, over the shoal regions where stratification is more inhibited by tidal mixing, there is greater friction and the transition from ebb to flood occurs more rapidly. The resulting residual circulation is seaward over the channel and landward over the shoal. The shoal–channel segregation of this barotropically induced estuarine residual flow is opposite to that typically associated with baroclinic estuarine circulation over channel–shoal bathymetry.
    Description: Support for this research was provided by the National Science Foundation Division of Ocean Sciences Grant OCE- 9984941.
    Keywords: Tides ; Ocean circulation ; Estuaries ; Turbulence
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  • 8
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2007. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography. 37 (2007): 2363-2386, doi:10.1175/jpo3118.1.
    Description: Intrinsic low-frequency variability is studied in the idealized, quasigeostrophic, midlatitude, wind-driven ocean gyres operating at large Reynolds number. A robust decadal variability mode driven by the transient mesoscale eddies is found and analyzed. The variability is a turbulent phenomenon, which is driven by the competition between the eddy rectification process and the potential vorticity anomalies induced by changes of the intergyre transport
    Description: Funding for Pavel Berloff was provided by NSF Grants OCE-0091836 and OCE- 0344094, by the U.K. Royal Society Fellowship, and by the Newton Trust Award, A. M. Hogg was supported by an Australian Research Council Postdoctoral Fellowship (DP0449851) during this work, and William K. Dewar was supported by NSF Grants OCE-0424227 and OCE-0550139.
    Keywords: Turbulence ; Gyres ; Transport ; Potential vorticity ; Mesoscale processes
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  • 9
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2011. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 41 (2011): 166-185, doi:10.1175/2010JPO4470.1.
    Description: Field observations of turbulent kinetic energy (TKE), dissipation rate ε, and turbulent length scale demonstrate the impact of both density stratification and nonlocal turbulent production on turbulent momentum flux. The data were collected in a highly stratified salt wedge estuary using the Mobile Array for Sensing Turbulence (MAST). Estimates of the dominant length scale of turbulent motions obtained from the vertical velocity spectra provide field confirmation of the theoretical limitation imposed by either the distance to the boundary or the Ozmidov scale, whichever is smaller. Under boundary-limited conditions, anisotropy generally increases with increasing shear and decreased distance to the boundary. Under Ozmidov-limited conditions, anisotropy increases rapidly when the gradient Richardson number exceeds 0.25. Both boundary-limited and Ozmidov-limited conditions demonstrate significant deviations from a local production–dissipation balance that are largely consistent with simple scaling relationships for the vertical divergence in TKE flux. Both the impact of stratification and deviation from equilibrium turbulence observed in the data are largely consistent with commonly used turbulence closure models that employ “nonequilibrium” stability functions. The data compare most favorably with the nonequilibrium version of the L. H. Kantha and C. A. Clayson stability functions. Not only is this approach more consistent with the observed critical gradient Richardson number of 0.25, but it also accounts for the large deviations from equilibrium turbulence in a manner consistent with the observations.
    Description: The funding for this research was obtained from ONR Grant N00014-06-1-0292 and NSF Grants and OCE-08-25226 and OCE-08-24871.
    Keywords: Turbulence ; Estuaries ; Kinetic energy
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  • 10
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2012. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 42 (2012): 855–868, doi:10.1175/JPO-D-10-05010.1.
    Description: Data from the Hudson River estuary demonstrate that the tidal variations in vertical salinity stratification are not consistent with the patterns associated with along-channel tidal straining. These observations result from three additional processes not accounted for in the traditional tidal straining model: 1) along-channel and 2) lateral advection of horizontal gradients in the vertical salinity gradient and 3) tidal asymmetries in the strength of vertical mixing. As a result, cross-sectionally averaged values of the vertical salinity gradient are shown to increase during the flood tide and decrease during the ebb. Only over a limited portion of the cross section does the observed stratification increase during the ebb and decrease during the flood. These observations highlight the three-dimensional nature of estuarine flows and demonstrate that lateral circulation provides an alternate mechanism that allows for the exchange of materials between surface and bottom waters, even when direct turbulent mixing through the pycnocline is prohibited by strong stratification.
    Description: The funding for this research was obtained from NSF Grant OCE-08-25226.
    Description: 2012-11-01
    Keywords: Mixing ; Ocean circulation ; Shear structure/flows ; Transport ; Turbulence
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  • 11
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2013. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 43 (2013): 259–282, doi:10.1175/JPO-D-11-0194.1.
    Description: This study reports on observations of turbulent dissipation and internal wave-scale flow properties in a standing meander of the Antarctic Circumpolar Current (ACC) north of the Kerguelen Plateau. The authors characterize the intensity and spatial distribution of the observed turbulent dissipation and the derived turbulent mixing, and consider underpinning mechanisms in the context of the internal wave field and the processes governing the waves’ generation and evolution. The turbulent dissipation rate and the derived diapycnal diffusivity are highly variable with systematic depth dependence. The dissipation rate is generally enhanced in the upper 1000–1500 m of the water column, and both the dissipation rate and diapycnal diffusivity are enhanced in some places near the seafloor, commonly in regions of rough topography and in the vicinity of strong bottom flows associated with the ACC jets. Turbulent dissipation is high in regions where internal wave energy is high, consistent with the idea that interior dissipation is related to a breaking internal wave field. Elevated turbulence occurs in association with downward-propagating near-inertial waves within 1–2 km of the surface, as well as with upward-propagating, relatively high-frequency waves within 1–2 km of the seafloor. While an interpretation of these near-bottom waves as lee waves generated by ACC jets flowing over small-scale topographic roughness is supported by the qualitative match between the spatial patterns in predicted lee wave radiation and observed near-bottom dissipation, the observed dissipation is found to be only a small percentage of the energy flux predicted by theory. The mismatch suggests an alternative fate to local dissipation for a significant fraction of the radiated energy.
    Description: SW acknowledges the support of the Grantham Institute for Climate Change, Imperial College London. ACNG acknowledges the support of a NERC Advanced Research Fellowship (Grant NE/C517633/1). KLP acknowledges support from Woods Hole Oceanographic Institution bridge support funds.
    Description: 2013-08-01
    Keywords: Diapycnal mixing ; Internal waves ; Turbulence
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  • 12
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2018. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 48 (2018): 905-923, doi:10.1175/JPO-D-17-0133.1.
    Description: Observations of turbulent kinetic energy, dissipation, and turbulent stress were collected in the middle reaches of Chesapeake Bay and were used to assess second-moment closure predictions of turbulence generated beneath breaking waves. Dissipation scaling indicates that the turbulent flow structure observed during a 10-day wind event was dominated by a three-layer response that consisted of 1) a wave transport layer, 2) a surface log layer, and 3) a tidal, bottom boundary layer limited by stable stratification. Below the wave transport layer, turbulent mixing was limited by stable stratification. Within the wave transport layer, where dissipation was balanced by a divergence in the vertical turbulent kinetic energy flux, the eddy viscosity was significantly underestimated by second-moment turbulence closure models, suggesting that breaking waves homogenized the mixed surface layer to a greater extent than the simple model of TKE diffusing away from a source at the surface. While the turbulent transport of TKE occurred largely downgradient, the intermittent downward sweeps of momentum generated by breaking waves occurred largely independent of the mean shear. The underprediction of stress in the wave transport layer by second-moment closures was likely due to the inability of the eddy viscosity model to capture the nonlocal turbulent transport of the momentum flux beneath breaking waves. Finally, the authors hypothesize that large-scale coherent turbulent eddies played a significant role in transporting momentum generated near the surface to depth.
    Description: This work was supported by National Science Foundation Grants OCE-1061609 and OCE-1339032.
    Description: 2018-10-19
    Keywords: Mixing ; Turbulence ; Waves, oceanic ; Boundary layer
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  • 13
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2018. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 48 (2018): 1815-1830, doi:10.1175/JPO-D-17-0275.1.
    Description: Recent progress in direct numerical simulations (DNSs) of stratified turbulent flows has led to increasing attention to the validity of the constancy of the dissipation flux coefficient Γ in the Osborn’s eddy diffusivity model. Motivated by lack of observational estimates of Γ, particularly under weakly stratified deep-ocean conditions, this study estimates Γ using deep microstructure profiles collected in various regions of the North Pacific and Southern Oceans. It is shown that Γ is not constant but varies significantly with the Ozmidov/Thorpe scale ratio ROT in a fashion similar to that obtained by previous DNS studies. Efficient mixing events with Γ ~ O(1) and ROT ~ O(0.1) tend to be frequently observed in the deep ocean (i.e., weak stratification), while moderate mixing events with Γ ~ O(0.1) and ROT ~ O(1) tend to be observed in the upper ocean (i.e., strong stratification). The observed negative relationship between Γ and ROT is consistent with a simple scaling that can be derived from classical turbulence theories. In contrast, the observed results exhibit no definite relationships between Γ and the buoyancy Reynolds number Reb, although Reb has long been thought to be another key parameter that controls Γ.
    Description: This study was supported by MEXT KAKENHI Grant JP15H05824 and JSPS KAKENHI Grant JP15H02131.
    Description: 2019-02-15
    Keywords: Abyssal circulation ; Mixing ; Subgrid-scale processes ; Turbulence ; In situ oceanic observations
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  • 14
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2018. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 48 (2018):1941-1950, doi:10.1175/JPO-D-17-0194.1.
    Description: Subglacial discharges have been observed to generate buoyant plumes along the ice face of Greenland tidewater glaciers. These plumes have been traditionally modeled using classical plume theory, and their characteristic parameters (e.g., velocity) are employed in the widely used three-equation melt parameterization. However, the applicability of plume theory for three-dimensional turbulent wall plumes is questionable because of the complex near-wall plume dynamics. In this study, corrections to the classical plume theory are introduced to account for the presence of a wall. In particular, the drag and entrainment coefficients are quantified for a three-dimensional turbulent wall plume using data from direct numerical simulations. The drag coefficient is found to be an order of magnitude larger than that for a boundary layer flow over a flat plate at a similar Reynolds number. This result suggests a significant increase in the melting estimates by the current parameterization. However, the volume flux in a wall plume is found to be one-half that of a conical plume that has 2 times the buoyancy flux. This finding suggests that the total entrainment (per unit area) of ambient water is the same and that the plume scalar characteristics (i.e., temperature and salinity) can be predicted reasonably well using classical plume theory.
    Description: This work was supported by the Linné FLOW Centre at KTH and the Academy of Finland Center of Excellence Programme Grant 307331 (author Ezhova) and by VR Swedish Research Council GrantVR2014-5001 (author Brandt). Support to author Cenedese was given by NSF Project OCE-1434041.
    Description: 2019-02-27
    Keywords: Buoyancy ; Entrainment ; Turbulence
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  • 15
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2011. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 41 (2011): 2223–2241, doi:10.1175/2011JPO4344.1.
    Description: Results are presented from an observational study of stratified, turbulent flow in the bottom boundary layer on the outer southeast Florida shelf. Measurements of momentum and heat fluxes were made using an array of acoustic Doppler velocimeters and fast-response temperature sensors in the bottom 3 m over a rough reef slope. Direct estimates of flux Richardson number Rf confirm previous laboratory, numerical, and observational work, which find mixing efficiency not to be a constant but rather to vary with Frt, Reb, and Rig. These results depart from previous observations in that the highest levels of mixing efficiency occur for Frt 〈 1, suggesting that efficient mixing can also happen in regions of buoyancy-controlled turbulence. Generally, the authors find that turbulence in the reef bottom boundary layer is highly variable in time and modified by near-bed flow, shear, and stratification driven by shoaling internal waves.
    Description: Funding was provided by grants from the National Oceanic and Atmospheric Administration’s National Undersea Research Program, National Science Foundation Grants OCE-0622967 and OCE- 0824972 to SGM, and the Singapore Stanford Program. Kristen Davis was supported by a National Defense Science and Engineering Graduate Fellowship and an ARCS Foundation Fellowship.
    Keywords: Boundary layer ; Turbulence ; Bottom currents ; Mixing ; Internal waves
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  • 16
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2015. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 45 (2015): 2381–2406, doi:10.1175/JPO-D-14-0086.1.
    Description: While near-inertial waves are known to be generated by atmospheric storms, recent observations in the Kuroshio Front find intense near-inertial internal-wave shear along sloping isopycnals, even during calm weather. Recent literature suggests that spontaneous generation of near-inertial waves by frontal instabilities could represent a major sink for the subinertial quasigeostrophic circulation. An unforced three-dimensional 1-km-resolution model, initialized with the observed cross-Kuroshio structure, is used to explore this mechanism. After several weeks, the model exhibits growth of 10–100-km-scale frontal meanders, accompanied by O(10) mW m−2 spontaneous generation of near-inertial waves associated with readjustment of submesoscale fronts forced out of balance by mesoscale confluent flows. These waves have properties resembling those in the observations. However, they are reabsorbed into the model Kuroshio Front with no more than 15% dissipating or radiating away. Thus, spontaneous generation of near-inertial waves represents a redistribution of quasigeostrophic energy rather than a significant sink.
    Description: “The Study of Kuroshio Ecosystem Dynamics for Sustainable Fisheries (SKED)” supported by MEXT, MIT-Hayashi Seed Fund, ONR (Awards N000140910196 and N000141210101), NSF (Award OCE 0928617, 0928138) for support.
    Description: 2016-03-01
    Keywords: Circulation/ Dynamics ; Frontogenesis/frontolysis ; Fronts ; Internal waves ; Turbulence ; Upwelling/downwelling ; Atm/Ocean Structure/ Phenomena ; Jets
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  • 17
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2015. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 45 (2015): 2497–2521, doi:10.1175/JPO-D-14-0128.1.
    Description: Oceanic density overturns are commonly used to parameterize the dissipation rate of turbulent kinetic energy. This method assumes a linear scaling between the Thorpe length scale LT and the Ozmidov length scale LO. Historic evidence supporting LT ~ LO has been shown for relatively weak shear-driven turbulence of the thermocline; however, little support for the method exists in regions of turbulence driven by the convective collapse of topographically influenced overturns that are large by open-ocean standards. This study presents a direct comparison of LT and LO, using vertical profiles of temperature and microstructure shear collected in the Luzon Strait—a site characterized by topographically influenced overturns up to O(100) m in scale. The comparison is also done for open-ocean sites in the Brazil basin and North Atlantic where overturns are generally smaller and due to different processes. A key result is that LT/LO increases with overturn size in a fashion similar to that observed in numerical studies of Kelvin–Helmholtz (K–H) instabilities for all sites but is most clear in data from the Luzon Strait. Resultant bias in parameterized dissipation is mitigated by ensemble averaging; however, a positive bias appears when instantaneous observations are depth and time integrated. For a series of profiles taken during a spring tidal period in the Luzon Strait, the integrated value is nearly an order of magnitude larger than that based on the microstructure observations. Physical arguments supporting LT ~ LO are revisited, and conceptual regimes explaining the relationship between LT/LO and a nondimensional overturn size are proposed. In a companion paper, Scotti obtains similar conclusions from energetics arguments and simulations.
    Description: B.D.M. and S.K.V. gratefully acknowledge the support of the Office of Naval Research under Grants N00014-12-1-0279, N00014-12-1-0282, and N00014-12-1-0938 (Program Manager: Dr. Terri Paluszkiewicz). S.K.V. also acknowledges support of the National Science Foundation under Grant OCE-1151838. L.S.L. acknowledges support for BBTRE by the National Science Foundation by Contract OCE94-15589 and NATRE and IWISE by the Office of Naval Research by Contracts N00014-92-1323 and N00014-10-10315. J.N.M. was supported through Grant 1256620 from the National Science Foundation and the Office of Naval Research (IWISE Project).
    Description: 2016-04-01
    Keywords: Circulation/ Dynamics ; Diapycnal mixing ; Small scale processes ; Turbulence ; Atm/Ocean Structure/ Phenomena ; Mixing ; Observational techniques and algorithms ; Profilers, oceanic ; Models and modeling ; Parameterization
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  • 18
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2015. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 45 (2015): 2621–2639, doi:10.1175/JPO-D-14-0239.1.
    Description: Measurements made as part of a large-scale experiment to examine wind-driven circulation and mixing in Chesapeake Bay demonstrate that circulations consistent with Langmuir circulation play an important role in surface boundary layer dynamics. Under conditions when the turbulent Langmuir number Lat is low (〈0.5), the surface mixed layer is characterized by 1) elevated vertical turbulent kinetic energy; 2) decreased anisotropy; 3) negative vertical velocity skewness indicative of strong/narrow downwelling and weak/broad upwelling; and 4) strong negative correlations between low-frequency vertical velocity and the velocity in the direction of wave propagation. These characteristics appear to be primarily the result of the vortex force associated with the surface wave field, but convection driven by a destabilizing heat flux is observed and appears to contribute significantly to the observed negative vertical velocity skewness. Conditions that favor convection usually also have strong Langmuir forcing, and these two processes probably both contribute to the surface mixed layer turbulence. Conditions in which traditional stress-driven turbulence is important are limited in this dataset. Unlike other shallow coastal systems where full water column Langmuir circulation has been observed, the salinity stratification in Chesapeake Bay is nearly always strong enough to prevent full-depth circulation from developing.
    Description: The funding for this research was provided by the National Science Foundation Grants OCE-1339032 and OCE-1338518.
    Description: 2016-04-01
    Keywords: Circulation/ Dynamics ; Convection ; Instability ; Mixing ; Turbulence ; Wave breaking ; Wind stress
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  • 19
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2016. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 46 (2016): 3155-3163, doi:10.1175/JPO-D-16-0123.1.
    Description: Idealized laboratory experiments have been conducted in a two-layer stratified fluid to investigate the leading-order dynamics that control submarine melting and meltwater export near a vertical ice–ocean interface as a function of subglacial discharge. In summer, the discharge of surface runoff at the base of a glacier (subglacial discharge) generates strong buoyant plumes that rise along the glacier front entraining ambient water along the way. The entrainment enhances the heat transport toward the glacier front and hence the submarine melt rate increases with the subglacial discharge rate. In the laboratory, the effect of subglacial discharge is simulated by introducing freshwater at freezing temperature from a point source at the base of an ice block representing the glacier. The circulation pattern observed both with and without subglacial discharge resembles those observed in previous observational and numerical studies. Buoyant plumes rise vertically until they find either their neutrally buoyant level or the free surface. Hence, the meltwater can deposit within the interior of the water column and not entirely at the free surface, as confirmed by field observations. The heat budget in the tank, calculated following a new framework, gives estimates of submarine melt rate that increase with the subglacial discharge and are in agreement with the directly measured submarine melting. This laboratory study provides the first direct measurements of submarine melt rates for different subglacial discharges, and the results are consistent with the predictions of previous theoretical and numerical studies.
    Description: Support to C. C. was given by the NSF project OCE- 1130008 and OCE-1434041. M. G. received support from the ‘‘Gori’’ Fellowship.
    Description: 2017-04-07
    Keywords: Glaciers ; Buoyancy ; Density currents ; Turbulence ; Laboratory/physical models
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  • 20
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2010. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 40 (2010): 2381-2400, doi:10.1175/2010JPO4403.1.
    Description: Langmuir circulation (LC) is a turbulent upper-ocean process driven by wind and surface waves that contributes significantly to the transport of momentum, heat, and mass in the oceanic surface layer. The authors have previously performed a direct comparison of large-eddy simulations and observations of the upper-ocean response to a wind event with rapid mixed layer deepening. The evolution of simulated crosswind velocity variance and spatial scales, as well as mixed layer deepening, was only consistent with observations if LC effects are included in the model. Based on an analysis of these validated simulations, in this study the fundamental differences in mixing between purely shear-driven turbulence and turbulence with LC are identified. In the former case, turbulent kinetic energy (TKE) production due to shear instabilities is largest near the surface, gradually decreasing to zero near the base of the mixed layer. This stands in contrast to the LC case in which at middepth range TKE production can be dominated by Stokes drift shear. Furthermore, the Eulerian mean vertical shear peaks near the base of the mixed layer so that TKE production by mean shear flow is elevated there. LC transports horizontal momentum efficiently downward leading to an along-wind velocity jet below LC downwelling regions at the base of the mixed layer. Locally enhanced vertical shear instabilities as a result of this jet efficiently erode the thermocline. In turn, enhanced breaking internal waves inject cold deep water into the mixed layer, where LC currents transport temperature perturbation advectively. Thus, LC and locally generated shear instabilities work intimately together to facilitate strongly the mixed layer deepening process.
    Description: This research was supported by the Office of Naval Research through Grants N00014-09-M-0112 (TK) and N00014-06-1-0178 (AP, JT). Author TK also received support from a Woods Hole Oceanographic Institution Cooperative Institute for Climate and Ocean Research Postdoctoral Scholarship.
    Keywords: Mixed layer ; Shear structure/flows ; Wind effects ; Turbulence ; Thermocline ; Internal waves ; Advection
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  • 21
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2013. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 43 (2013): 1841–1861, doi:10.1175/JPO-D-12-0231.1.
    Description: In this idealized numerical modeling study, the composition of residual sediment fluxes in energetic (e.g., weakly or periodically stratified) tidal estuaries is investigated by means of one-dimensional water column models, with some focus on the sediment availability. Scaling of the underlying dynamic equations shows dependence of the results on the Simpson number (relative strength of horizontal density gradient) and the Rouse number (relative settling velocity) as well as impacts of the Unsteadiness number (relative tidal frequency). Here, the parameter space given by the Simpson and Rouse numbers is mainly investigated. A simple analytical model based on the assumption of stationarity shows that for small Simpson and Rouse numbers sediment flux is down estuary and vice versa for large Simpson and Rouse numbers. A fully dynamic water column model coupled to a second-moment turbulence closure model allows to decompose the sediment flux profiles into contributions from the transport flux (product of subtidal velocity and sediment concentration profiles) and the fluctuation flux profiles (tidal covariance between current velocity and sediment concentration). Three different types of bottom sediment pools are distinguished to vary the sediment availability, by defining a time scale for complete sediment erosion. For short erosion times scales, the transport sediment flux may dominate, but for larger erosion time scales the fluctuation sediment flux largely dominates the tidal sediment flux. When quarter-diurnal components are added to the tidal forcing, up-estuary sediment fluxes are strongly increased for stronger and shorter flood tides and vice versa. The theoretical results are compared to field observations in a tidally energetic inlet.
    Description: Project funding was provided by the German Research Foundation (DFG) in the framework of the Project ECOWS (Role of Estuarine Circulation for Transport of Suspended Particulate Matter in the Wadden Sea, BU 1199/11) and by the German Federal Ministry of Research and Education in the framework of the Project PACE [The future of the Wadden Sea sediment fluxes: still keeping pace with sea level rise? (FKZ 03F0634A)].
    Description: 2014-03-01
    Keywords: Channel flows ; Coastal flows ; Mixing ; Transport ; Turbulence ; Single column models
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  • 22
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2014. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 44 (2014): 1466–1492, doi:10.1175/JPO-D-12-0154.1.
    Description: Simultaneous full-depth microstructure measurements of turbulence and finestructure measurements of velocity and density are analyzed to investigate the relationship between turbulence and the internal wave field in the Antarctic Circumpolar Current. These data reveal a systematic near-bottom overprediction of the turbulent kinetic energy dissipation rate by finescale parameterization methods in select locations. Sites of near-bottom overprediction are typically characterized by large near-bottom flow speeds and elevated topographic roughness. Further, lower-than-average shear-to-strain ratios indicative of a less near-inertial wave field, rotary spectra suggesting a predominance of upward internal wave energy propagation, and enhanced narrowband variance at vertical wavelengths on the order of 100 m are found at these locations. Finally, finescale overprediction is typically associated with elevated Froude numbers based on the near-bottom shear of the background flow, and a background flow with a systematic backing tendency. Agreement of microstructure- and finestructure-based estimates within the expected uncertainty of the parameterization away from these special sites, the reproducibility of the overprediction signal across various parameterization implementations, and an absence of indications of atypical instrument noise at sites of parameterization overprediction, all suggest that physics not encapsulated by the parameterization play a role in the fate of bottom-generated waves at these locations. Several plausible underpinning mechanisms based on the limited available evidence are discussed that offer guidance for future studies.
    Description: The SOFine project is funded by the United Kingdom’s Natural Environmental Research Council (NERC) (Grant NE/G001510/1). SW acknowledges the support of anARCDiscovery Early CareerResearchAward (Grant DE120102927), as well as the Grantham Institute for Climate Change, Imperial College London, and the ARC Centre of Excellence for Climate System Science (Grant CE110001028). ACNG acknowledges the support of a NERC Advanced Research Fellowship (Grant NE/C517633/1).KLP acknowledges support fromWoods Hole Oceanographic Institution bridge support funds.
    Description: 2014-11-01
    Keywords: Circulation/ Dynamics ; Diapycnal mixing ; Internal waves ; Small scale processes ; Turbulence ; Observational techniques and algorithms ; In situ oceanic observations ; Profilers, oceanic
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  • 23
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2014. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 44 (2014): 2593–2616, doi:10.1175/JPO-D-13-0120.1.
    Description: The first direct estimate of the rate at which geostrophic turbulence mixes tracers across the Antarctic Circumpolar Current is presented. The estimate is computed from the spreading of a tracer released upstream of Drake Passage as part of the Diapycnal and Isopycnal Mixing Experiment in the Southern Ocean (DIMES). The meridional eddy diffusivity, a measure of the rate at which the area of the tracer spreads along an isopycnal across the Antarctic Circumpolar Current, is 710 ± 260 m2 s−1 at 1500-m depth. The estimate is based on an extrapolation of the tracer-based diffusivity using output from numerical tracers released in a one-twentieth of a degree model simulation of the circulation and turbulence in the Drake Passage region. The model is shown to reproduce the observed spreading rate of the DIMES tracer and suggests that the meridional eddy diffusivity is weak in the upper kilometer of the water column with values below 500 m2 s−1 and peaks at the steering level, near 2 km, where the eddy phase speed is equal to the mean flow speed. These vertical variations are not captured by ocean models presently used for climate studies, but they significantly affect the ventilation of different water masses.
    Description: NSF support through Awards OCE-1233832, OCE-1232962, and OCE-1048926 is gratefully acknowledged.
    Description: 2015-04-01
    Keywords: Geographic location/entity ; Southern Ocean ; Circulation/ Dynamics ; Diffusion ; Eddies ; Ocean circulation ; Turbulence ; Physical Meteorology and Climatology ; Isopycnal mixing
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  • 24
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2016. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 46 (2016): 1309-1321, doi:10.1175/JPO-D-15-0068.1.
    Description: Direct measurements of oceanic turbulent parameters were taken upstream of and across Drake Passage, in the region of the Subantarctic and Polar Fronts. Values of turbulent kinetic energy dissipation rate ε estimated by microstructure are up to two orders of magnitude lower than previously published estimates in the upper 1000 m. Turbulence levels in Drake Passage are systematically higher than values upstream, regardless of season. The dissipation of thermal variance χ is enhanced at middepth throughout the surveys, with the highest values found in northern Drake Passage, where water mass variability is the most pronounced. Using the density ratio, evidence for double-diffusive instability is presented. Subject to double-diffusive physics, the estimates of diffusivity using the Osborn–Cox method are larger than ensemble statistics based on ε and the buoyancy frequency.
    Description: This work was supported by grants from the U.S. National Science Foundation.
    Description: 2016-10-05
    Keywords: Geographic location/entity ; Southern Ocean ; Circulation/ Dynamics ; Diapycnal mixing ; Mixing ; Turbulence ; Atm/Ocean Structure/ Phenomena ; Fronts ; Observational techniques and algorithms ; Profilers, oceanic
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  • 25
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2016. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 46 (2016): 1769-1783, doi:10.1175/JPO-D-15-0193.1.
    Description: High-resolution observations of velocity, salinity, and turbulence quantities were collected in a salt wedge estuary to quantify the efficiency of stratified mixing in a high-energy environment. During the ebb tide, a midwater column layer of strong shear and stratification developed, exhibiting near-critical gradient Richardson numbers and turbulent kinetic energy (TKE) dissipation rates greater than 10−4 m2 s−3, based on inertial subrange spectra. Collocated estimates of scalar variance dissipation from microconductivity sensors were used to estimate buoyancy flux and the flux Richardson number Rif. The majority of the samples were outside the boundary layer, based on the ratio of Ozmidov and boundary length scales, and had a mean Rif = 0.23 ± 0.01 (dissipation flux coefficient Γ = 0.30 ± 0.02) and a median gradient Richardson number Rig = 0.25. The boundary-influenced subset of the data had decreased efficiency, with Rif = 0.17 ± 0.02 (Γ = 0.20 ± 0.03) and median Rig = 0.16. The relationship between Rif and Rig was consistent with a turbulent Prandtl number of 1. Acoustic backscatter imagery revealed coherent braids in the mixing layer during the early ebb and a transition to more homogeneous turbulence in the midebb. A temporal trend in efficiency was also visible, with higher efficiency in the early ebb and lower efficiency in the late ebb when the bottom boundary layer had greater influence on the flow. These findings show that mixing efficiency of turbulence in a continuously forced, energetic, free shear layer can be significantly greater than the broadly cited upper bound from Osborn of 0.15–0.17.
    Description: Holleman was supported by the Devonshire Scholars program. The field study and the coauthors’ contributions were supported by NSF Grant OCE 0926427.
    Description: 2016-11-24
    Keywords: Circulation/ Dynamics ; Mixing ; Shear structure/flows ; Turbulence ; Observational techniques and algorithms ; Ship observations
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  • 26
    Publication Date: 2022-05-26
    Description: © The Author(s), 2016. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Journal of Atmospheric and Oceanic Technology 33 (2016): 873-890, doi:10.1175/JTECH-D-15-0109.1.
    Description: Direct covariance flux (DCF) measurements taken from floating platforms are contaminated by wave-induced platform motions that need to be removed before computation of the turbulent fluxes. Several correction algorithms have been developed and successfully applied in earlier studies from research vessels and, most recently, by the use of moored buoys. The validation of those correction algorithms has so far been limited to short-duration comparisons against other floating platforms. Although these comparisons show in general a good agreement, there is still a lack of a rigorous validation of the method, required to understand the strengths and weaknesses of the existing motion-correction algorithms. This paper attempts to provide such a validation by a comparison of flux estimates from two DCF systems, one mounted on a moored buoy and one on the Air–Sea Interaction Tower (ASIT) at the Martha’s Vineyard Coastal Observatory, Massachusetts. The ASIT was specifically designed to minimize flow distortion over a wide range of wind directions from the open ocean for flux measurements. The flow measurements from the buoy system are corrected for wave-induced platform motions before computation of the turbulent heat and momentum fluxes. Flux estimates and cospectra of the corrected buoy data are found to be in very good agreement with those obtained from the ASIT. The comparison is also used to optimize the filter constants used in the motion-correction algorithm. The quantitative agreement between the buoy data and the ASIT demonstrates that the DCF method is applicable for turbulence measurements from small moving platforms, such as buoys.
    Description: This work was funded by the National Science Foundation Grant OCE04-24536 as part of the CLIVAR Mode Water Dynamic Experiment (CLIMODE).
    Keywords: Circulation/ Dynamics ; Turbulence ; Atm/Ocean Structure/ Phenomena ; Boundary layer ; Physical Meteorology and Climatology ; Air-sea interaction ; Observational techniques and algorithms ; Buoy observations ; Quality assurance/control
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  • 27
    Publication Date: 2022-10-12
    Description: Author Posting. © American Meteorological Society, 2022. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 52(10), (2022): 2325–2341, https://doi.org/10.1175/jpo-d-21-0015.1.
    Description: The ocean surface boundary layer is a gateway of energy transfer into the ocean. Wind-driven shear and meteorologically forced convection inject turbulent kinetic energy into the surface boundary layer, mixing the upper ocean and transforming its density structure. In the absence of direct observations or the capability to resolve subgrid-scale 3D turbulence in operational ocean models, the oceanography community relies on surface boundary layer similarity scalings (BLS) of shear and convective turbulence to represent this mixing. Despite their importance, near-surface mixing processes (and ubiquitous BLS representations of these processes) have been undersampled in high-energy forcing regimes such as the Southern Ocean. With the maturing of autonomous sampling platforms, there is now an opportunity to collect high-resolution spatial and temporal measurements in the full range of forcing conditions. Here, we characterize near-surface turbulence under strong wind forcing using the first long-duration glider microstructure survey of the Southern Ocean. We leverage these data to show that the measured turbulence is significantly higher than standard shear-convective BLS in the shallower parts of the surface boundary layer and lower than standard shear-convective BLS in the deeper parts of the surface boundary layer; the latter of which is not easily explained by present wave-effect literature. Consistent with the CBLAST (Coupled Boundary Layers and Air Sea Transfer) low winds experiment, this bias has the largest magnitude and spread in the shallowest 10% of the actively mixing layer under low-wind and breaking wave conditions, when relatively low levels of turbulent kinetic energy (TKE) in surface regime are easily biased by wave events.
    Description: This paper is VIMS Contribution 4103. Computational resources were provided by the VIMS Ocean-Atmosphere and Climate Change Research Fund. AUSSOM was supported by the OCE Division of the National Science Foundation (1558639).
    Keywords: Turbulence ; Wind shear ; Boundary layer ; Parameterization
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  • 28
    Publication Date: 2022-05-27
    Description: Author Posting. © American Meteorological Society, 2021. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 51(1), (2021): 19-35, https://doi.org/10.1175/JPO-D-19-0233.1.
    Description: In the Beaufort Sea in September of 2015, concurrent mooring and microstructure observations were used to assess dissipation rates in the vicinity of 72°35′N, 145°1′W. Microstructure measurements from a free-falling profiler survey showed very low [O(10−10) W kg−1] turbulent kinetic energy dissipation rates ε. A finescale parameterization based on both shear and strain measurements was applied to estimate the ratio of shear to strain Rω and ε at the mooring location, and a strain-based parameterization was applied to the microstructure survey (which occurred approximately 100 km away from the mooring site) for direct comparison with microstructure results. The finescale parameterization worked well, with discrepancies ranging from a factor of 1–2.5 depending on depth. The largest discrepancies occurred at depths with high shear. Mean Rω was 17, and Rω showed high variability with values ranging from 3 to 50 over 8 days. Observed ε was slightly elevated (factor of 2–3 compared with a later survey of 11 profiles taken over 3 h) from 25 to 125 m following a wind event which occurred at the beginning of the mooring deployment, reaching a maximum of ε= 6 × 10−10 W kg−1 at 30-m depth. Velocity signals associated with near-inertial waves (NIWs) were observed at depths greater than 200 m, where the Atlantic Water mass represents a reservoir of oceanic heat. However, no evidence of elevated ε or heat fluxes was observed in association with NIWs at these depths in either the microstructure survey or the finescale parameterization estimates.
    Description: This work was supported by NSF Grants PLR 14-56705 and PLR-1303791 and by NSF Graduate Research Fellowship Grant DGE-1650112.
    Keywords: Ocean ; Arctic ; Internal waves ; Turbulence ; Diapycnal mixing
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  • 29
    Publication Date: 2022-05-27
    Description: © The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Spingys, C. P., Garabato, A. C. N., Legg, S., Polzin, K. L., Abrahamsen, E. P., Buckingham, C. E., Forryan, A., & Frajka-Williams, E. E. Mixing and transformation in a deep western boundary current: a case study. Journal of Physical Oceanography, 51(4), (2021): 1205-1222, https://doi.org/10.1175/JPO-D-20-0132.1
    Description: Water-mass transformation by turbulent mixing is a key part of the deep-ocean overturning, as it drives the upwelling of dense waters formed at high latitudes. Here, we quantify this transformation and its underpinning processes in a small Southern Ocean basin: the Orkney Deep. Observations reveal a focusing of the transport in density space as a deep western boundary current (DWBC) flows through the region, associated with lightening and densification of the current’s denser and lighter layers, respectively. These transformations are driven by vigorous turbulent mixing. Comparing this transformation with measurements of the rate of turbulent kinetic energy dissipation indicates that, within the DWBC, turbulence operates with a high mixing efficiency, characterized by a dissipation ratio of 0.6 to 1 that exceeds the common value of 0.2. This result is corroborated by estimates of the dissipation ratio from microstructure observations. The causes of the transformation are unraveled through a decomposition into contributions dependent on the gradients in density space of the: dianeutral mixing rate, isoneutral area, and stratification. The transformation is found to be primarily driven by strong turbulence acting on an abrupt transition from the weakly stratified bottom boundary layer to well-stratified off-boundary waters. The reduced boundary layer stratification is generated by a downslope Ekman flow associated with the DWBC’s flow along sloping topography, and is further regulated by submesoscale instabilities acting to restratify near-boundary waters. Our results provide observational evidence endorsing the importance of near-boundary mixing processes to deep-ocean overturning, and highlight the role of DWBCs as hot spots of dianeutral upwelling.
    Description: CS, ACNG, AF, and EFW were supported by the U.K. Natural Environment Research Council (NERC) Grant NE/K013181/1. ACNG was supported by the Royal Society and Wolfson Foundation. EPA and CEB were supported by NERC Grant NE/K012843/1. CEB was funded by an MSCA grant (No. 798319) from the European Union’s Horizon 2020 program. EPA was supported by NERC Grant NE/N018095/1. SL and KP were supported by U.S. National Science Foundation Grants OCE-1536453 and OCE-1536779. SL acknowledges support of Award NA18OAR4320123 from the National Oceanic and Atmospheric Administration, U.S. Department of Commerce. The statements, findings, conclusions, and recommendations are those of the authors, and do not necessarily reflect the views of the National Oceanic and Atmospheric Administration, or the U.S. Department of Commerce.
    Keywords: Bottom currents ; Diapycnal mixing ; Turbulence ; Southern Ocean
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  • 30
    Publication Date: 2022-09-15
    Description: Author Posting. © American Meteorological Society, 2022. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 52(1),(2022): 75–97, https://doi.org/10.1175/JPO-D-21-0099.1.
    Description: Mesoscale eddies contain the bulk of the ocean’s kinetic energy (KE), but fundamental questions remain on the cross-scale KE transfers linking eddy generation and dissipation. The role of submesoscale flows represents the key point of discussion, with contrasting views of submesoscales as either a source or a sink of mesoscale KE. Here, the first observational assessment of the annual cycle of the KE transfer between mesoscale and submesoscale motions is performed in the upper layers of a typical open-ocean region. Although these diagnostics have marginal statistical significance and should be regarded cautiously, they are physically plausible and can provide a valuable benchmark for model evaluation. The cross-scale KE transfer exhibits two distinct stages, whereby submesoscales energize mesoscales in winter and drain mesoscales in spring. Despite this seasonal reversal, an inverse KE cascade operates throughout the year across much of the mesoscale range. Our results are not incompatible with recent modeling investigations that place the headwaters of the inverse KE cascade at the submesoscale, and that rationalize the seasonality of mesoscale KE as an inverse cascade-mediated response to the generation of submesoscales in winter. However, our findings may challenge those investigations by suggesting that, in spring, a downscale KE transfer could dampen the inverse KE cascade. An exploratory appraisal of the dynamics governing mesoscale–submesoscale KE exchanges suggests that the upscale KE transfer in winter is underpinned by mixed layer baroclinic instabilities, and that the downscale KE transfer in spring is associated with frontogenesis. Current submesoscale-permitting ocean models may substantially understate this downscale KE transfer, due to the models’ muted representation of frontogenesis.
    Description: The OSMOSIS experiment was funded by the U.K. Natural Environment Research Council (NERC) through Grants NE/1019999/1 and NE/101993X/1. ACNG acknowledges the support of the Royal Society and the Wolfson Foundation, and XY that of a China Scholarship Council PhD studentship.
    Keywords: Ageostrophic circulations ; Dynamics ; Eddies ; Energy transport ; Frontogenesis/frontolysis ; Instability ; Mesoscale processes ; Nonlinear dynamics ; Ocean circulation ; Ocean dynamics ; Small scale processes ; Turbulence
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  • 31
    Publication Date: 2022-09-01
    Description: Author Posting. © American Meteorological Society, 2022. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 52(8), (2022): 1677-1691, https://doi.org/10.1175/jpo-d-21-0269.1.
    Description: Oceanic mesoscale motions including eddies, meanders, fronts, and filaments comprise a dominant fraction of oceanic kinetic energy and contribute to the redistribution of tracers in the ocean such as heat, salt, and nutrients. This reservoir of mesoscale energy is regulated by the conversion of potential energy and transfers of kinetic energy across spatial scales. Whether and under what circumstances mesoscale turbulence precipitates forward or inverse cascades, and the rates of these cascades, remain difficult to directly observe and quantify despite their impacts on physical and biological processes. Here we use global observations to investigate the seasonality of surface kinetic energy and upper-ocean potential energy. We apply spatial filters to along-track satellite measurements of sea surface height to diagnose surface eddy kinetic energy across 60–300-km scales. A geographic and scale-dependent seasonal cycle appears throughout much of the midlatitudes, with eddy kinetic energy at scales less than 60 km peaking 1–4 months before that at 60–300-km scales. Spatial patterns in this lag align with geographic regions where an Argo-derived estimate of the conversion of potential to kinetic energy is seasonally varying. In midlatitudes, the conversion rate peaks 0–2 months prior to kinetic energy at scales less than 60 km. The consistent geographic patterns between the seasonality of potential energy conversion and kinetic energy across spatial scale provide observational evidence for the inverse cascade and demonstrate that some component of it is seasonally modulated. Implications for mesoscale parameterizations and numerical modeling are discussed.
    Description: This work was generously funded by NSF Grants OCE-1912302, OCE-1912125 (Drushka), and OCE-1912325 (Abernathey) as part of the Ocean Energy and Eddy Transport Climate Process Team.
    Keywords: Eddies ; Energy transport ; Mesoscale processes ; Turbulence ; Oceanic mixed layer ; Altimetry ; Seasonal cycle
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  • 32
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2016. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 46 (2016): 1823-1837, doi:10.1175/JPO-D-15-0165.1.
    Description: Measurements just beneath the ocean surface demonstrate that the primary mechanism by which energy from breaking waves is transmitted into the water column is through the work done by the covariance of turbulent pressure and velocity fluctuations. The convergence in the vertical transport of turbulent kinetic energy (TKE) balances the dissipation rate of TKE at first order and is nearly an order of magnitude greater than the sum of the integrated Eulerian and Stokes shear production. The measured TKE transport is consistent with a simple conceptual model that assumes roughly half of the surface flux of TKE by wave breaking is transmitted to depths greater than the significant wave height. During conditions when breaking waves are inferred, the direction of momentum flux is more aligned with the direction of wave propagation than with the wind direction. Both the energy and momentum fluxes occur at frequencies much lower than the wave band, consistent with the time scales associated with wave breaking. The largest instantaneous values of momentum flux are associated with strong downward vertical velocity perturbations, in contrast to the pressure work, which is associated with strong drops in pressure and upward vertical velocity perturbations.
    Description: Funding for this research was provided by the National Science Foundation Grants OCE-1339032 and OCE-1338518
    Keywords: Circulation/ Dynamics ; Energy transport ; Mixing ; Momentum ; Turbulence ; Wave breaking ; Waves, oceanic
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  • 33
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2014. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 44 (2014): 1306–1328, doi:10.1175/JPO-D-12-0191.1.
    Description: The ice–ocean system is investigated on inertial to monthly time scales using winter 2009–10 observations from the first ice-tethered profiler (ITP) equipped with a velocity sensor (ITP-V). Fluctuations in surface winds, ice velocity, and ocean velocity at 7-m depth were correlated. Observed ocean velocity was primarily directed to the right of the ice velocity and spiraled clockwise while decaying with depth through the mixed layer. Inertial and tidal motions of the ice and in the underlying ocean were observed throughout the record. Just below the ice–ocean interface, direct estimates of the turbulent vertical heat, salt, and momentum fluxes and the turbulent dissipation rate were obtained. Periods of elevated internal wave activity were associated with changes to the turbulent heat and salt fluxes as well as stratification primarily within the mixed layer. Turbulent heat and salt fluxes were correlated particularly when the mixed layer was closest to the freezing temperature. Momentum flux is adequately related to velocity shear using a constant ice–ocean drag coefficient, mixing length based on the planetary and geometric scales, or Rossby similarity theory. Ekman viscosity described velocity shear over the mixed layer. The ice–ocean drag coefficient was elevated for certain directions of the ice–ocean shear, implying an ice topography that was characterized by linear ridges. Mixing length was best estimated using the wavenumber of the beginning of the inertial subrange or a variable drag coefficient. Analyses of this and future ITP-V datasets will advance understanding of ice–ocean interactions and their parameterizations in numerical models.
    Description: Support for this study and the overall ITP program was provided by the National Science Foundation and Woods Hole Oceanographic Institution. Support for S. Cole was partially though the Postdoctoral Scholar Program at the Woods Hole Oceanographic Institution, with funding provided by the Devonshire Foundation.
    Description: 2014-11-01
    Keywords: Geographic location/entity ; Arctic ; Sea ice ; Circulation/ Dynamics ; Ekman pumping/transport ; Internal waves ; Turbulence ; Atm/Ocean Structure/ Phenomena ; Oceanic mixed layer
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  • 34
    Publication Date: 2022-06-10
    Description: Author Posting. © American Meteorological Society , 2021. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Zippel, S. F., Farrar, J. T., Zappa, C. J., Miller, U., St Laurent, L., Ijichi, T., Weller, R. A., McRaven, L., Nylund, S., & Le Bel, D. Moored turbulence measurements using pulse-coherent doppler sonar. Journal of Atmospheric and Oceanic Technology, 38(9), (2021): 1621–1639, https://doi.org/10.1175/JTECH-D-21-0005.1.
    Description: Upper-ocean turbulence is central to the exchanges of heat, momentum, and gases across the air–sea interface and therefore plays a large role in weather and climate. Current understanding of upper-ocean mixing is lacking, often leading models to misrepresent mixed layer depths and sea surface temperature. In part, progress has been limited by the difficulty of measuring turbulence from fixed moorings that can simultaneously measure surface fluxes and upper-ocean stratification over long time periods. Here we introduce a direct wavenumber method for measuring turbulent kinetic energy (TKE) dissipation rates ϵ from long-enduring moorings using pulse-coherent ADCPs. We discuss optimal programming of the ADCPs, a robust mechanical design for use on a mooring to maximize data return, and data processing techniques including phase-ambiguity unwrapping, spectral analysis, and a correction for instrument response. The method was used in the Salinity Processes Upper-Ocean Regional Study (SPURS) to collect two year-long datasets. We find that the mooring-derived TKE dissipation rates compare favorably to estimates made nearby from a microstructure shear probe mounted to a glider during its two separate 2-week missions for O(10−8) ≤ ϵ ≤ O(10−5) m2 s−3. Periods of disagreement between turbulence estimates from the two platforms coincide with differences in vertical temperature profiles, which may indicate that barrier layers can substantially modulate upper-ocean turbulence over horizontal scales of 1–10 km. We also find that dissipation estimates from two different moorings at 12.5 and at 7 m are in agreement with the surface buoyancy flux during periods of strong nighttime convection, consistent with classic boundary layer theory.
    Description: This work was funded by NASA as part of the Salinity Processes in the Upper Ocean Regional Study (SPURS), supporting field work for SPURS-1 (NASA Grant NNX11AE84G), for SPURS-2 (NASA Grant NNX15AG20G), and for analysis (NASA Grant 80NSSC18K1494). Funding for early iterations of this project associated with the VOCALS project and Stratus 9 mooring was provided by NSF (Awards 0745508 and 0745442). Additional funding was provided by ONR Grant N000141812431 and NSF Award 1756839. The Stratus Ocean Reference Station is funded by the Global Ocean Monitoring and Observing Program of the National Oceanic and Atmospheric Administration (CPO FundRef Number 100007298), through the Cooperative Institute for the North Atlantic Region (CINAR) under Cooperative Agreement NA14OAR4320158. Microstructure measurements made from the glider were supported by NSF (Award 1129646).
    Keywords: Ocean ; Turbulence ; Atmosphere-ocean interaction ; Boundary layer ; Oceanic mixed layer ; In situ oceanic observations
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  • 35
    Publication Date: 2022-06-13
    Description: © The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Fine, E., MacKinnon, J., Alford, M., Middleton, L., Taylor, J., Mickett, J., Cole, S., Couto, N., Boyer, A., & Peacock, T. Double diffusion, shear instabilities, and heat impacts of a pacific summer water intrusion in the Beaufort Sea. Journal of Physical Oceanography, 52(2), (2022): 189–203, https://doi.org/10.1175/jpo-d-21-0074.1.
    Description: Pacific Summer Water eddies and intrusions transport heat and salt from boundary regions into the western Arctic basin. Here we examine concurrent effects of lateral stirring and vertical mixing using microstructure data collected within a Pacific Summer Water intrusion with a length scale of ∼20 km. This intrusion was characterized by complex thermohaline structure in which warm Pacific Summer Water interleaved in alternating layers of O(1) m thickness with cooler water, due to lateral stirring and intrusive processes. Along interfaces between warm/salty and cold/freshwater masses, the density ratio was favorable to double-diffusive processes. The rate of dissipation of turbulent kinetic energy (ε) was elevated along the interleaving surfaces, with values up to 3 × 10−8 W kg−1 compared to background ε of less than 10−9 W kg−1. Based on the distribution of ε as a function of density ratio Rρ, we conclude that double-diffusive convection is largely responsible for the elevated ε observed over the survey. The lateral processes that created the layered thermohaline structure resulted in vertical thermohaline gradients susceptible to double-diffusive convection, resulting in upward vertical heat fluxes. Bulk vertical heat fluxes above the intrusion are estimated in the range of 0.2–1 W m−2, with the localized flux above the uppermost warm layer elevated to 2–10 W m−2. Lateral fluxes are much larger, estimated between 1000 and 5000 W m−2, and set an overall decay rate for the intrusion of 1–5 years.
    Description: This work was supported by ONR Grant N00014-16-1-2378 and NSF Grants PLR 14-56705 and PLR-1303791, NSF Graduate Research Fellowship Grant DGE-1650112, as well as by the Postdoctoral Scholar Program at Woods Hole Oceanographic Institution, with funding provided by the Weston Howland Jr. Postdoctoral Scholarship.
    Keywords: Arctic ; Diapycnal mixing ; Diffusion ; Fluxes ; Instability ; Mixing ; Turbulence
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  • 36
    Publication Date: 2022-05-26
    Description: © The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Cusack, J. M., Brearley, J. A., Garabato, A. C. N., Smeed, D. A., Polzin, K. L., Velzeboer, N., & Shakespeare, C. J. Observed eddy-internal wave interactions in the Southern Ocean. Journal of Physical Oceanography, 50(10), (2020): 3042-3062, doi:10.1175/JPO-D-20-0001.1.
    Description: The physical mechanisms that remove energy from the Southern Ocean’s vigorous mesoscale eddy field are not well understood. One proposed mechanism is direct energy transfer to the internal wave field in the ocean interior, via eddy-induced straining and shearing of preexisting internal waves. The magnitude, vertical structure, and temporal variability of the rate of energy transfer between eddies and internal waves is quantified from a 14-month deployment of a mooring cluster in the Scotia Sea. Velocity and buoyancy observations are decomposed into wave and eddy components, and the energy transfer is estimated using the Reynolds-averaged energy equation. We find that eddies gain energy from the internal wave field at a rate of −2.2 ± 0.6 mW m−2, integrated from the bottom to 566 m below the surface. This result can be decomposed into a positive (eddy to wave) component, equal to 0.2 ± 0.1 mW m−2, driven by horizontal straining of internal waves, and a negative (wave to eddy) component, equal to −2.5 ± 0.6 mW m−2, driven by vertical shearing of the wave spectrum. Temporal variability of the transfer rate is much greater than the mean value. Close to topography, large energy transfers are associated with low-frequency buoyancy fluxes, the underpinning physics of which do not conform to linear wave dynamics and are thereby in need of further research. Our work suggests that eddy–internal wave interactions may play a significant role in the energy balance of the Southern Ocean mesoscale eddy and internal wave fields.
    Description: Funding for DIMES was provided by U.K. Natural Environment Research Council (NERC) Grants NE/E007058/1 and NE/E005667/1. JMC acknowledges the support of a NERC PhD studentship, and ACNG that of the Royal Society and the Wolfson Foundation. NV acknowledges support from the ARC Centre of Excellence for Climate Extremes (CLEX) Honours Scholarship and the ANU PBSA Partnership - Spotless Scholarship. CJS acknowledges support from an ARC Discovery Early Career Researcher Award DE180100087 and an Australian National University Futures Scheme award. Numerical simulations were conducted on the National Computational Infrastructure (NCI) facility, Canberra, Australia. This study has been conducted using E.U. Copernicus Marine Service Information. We thank two anonymous reviewers for their comments which helped to improve the manuscript significantly. Codes and output files are available online at the project repository (https://github.com/jessecusack/DIMES_eddy_wave_interactions).
    Keywords: Southern Ocean ; Eddies ; Internal waves ; Turbulence
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  • 37
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2019. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 49(9), (2019): 2237-2254, doi: 10.1175/JPO-D-18-0181.1.
    Description: A cluster of 45 drifters deployed in the Bay of Bengal is tracked for a period of four months. Pair dispersion statistics, from observed drifter trajectories and simulated trajectories based on surface geostrophic velocity, are analyzed as a function of drifter separation and time. Pair dispersion suggests nonlocal dynamics at submesoscales of 1–20 km, likely controlled by the energetic mesoscale eddies present during the observations. Second-order velocity structure functions and their Helmholtz decomposition, however, suggest local dispersion and divergent horizontal flow at scales below 20 km. This inconsistency cannot be explained by inertial oscillations alone, as has been reported in recent studies, and is likely related to other nondispersive processes that impact structure functions but do not enter pair dispersion statistics. At scales comparable to the deformation radius LD, which is approximately 60 km, we find dynamics in agreement with Richardson’s law and observe local dispersion in both pair dispersion statistics and second-order velocity structure functions.
    Description: This research was supported by the Air Sea Interaction Regional Initiative (ASIRI) under ONR Grant N00014-13-1-0451 (SE and AM) and ONR Grant N00014-13-1-0477 (VH and LC). Additionally, AM and SE thank NSF (Grant OCE-I434788) and ONR (Grant N00014-16-1-2470) for support; VH and LC were further supported by ONR Grant N00014-15-1-2286 and NOAA GDP Grant NA10OAR4320156. We thank Joe LaCasce, Dhruv Balwada, and one anonymous reviewer for helpful comments and discussions that significantly improved this manuscript. The authors thank the captain and crew of the R/V Roger Revelle. The SVP-type drifters are part of the Global Drifter Program and supported by ONR Grant N00014-15-1-2286 and NOAA GDP Grant NA10OAR4320156 and are available under http://www.aoml.noaa.gov/phod/dac/. The Ssalto/Duacs altimeter products were produced and distributed by the Copernicus Marine and Environment Monitoring Service (CMEMS, http://www.marine.copernicus.eu).
    Keywords: Dispersion ; Fronts ; Mesoscale processes ; Subgrid-scale processes ; Trajectories ; Turbulence
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  • 38
    Publication Date: 2022-05-26
    Description: © The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Cusack, J. M., Voet, G., Alford, M. H., Girton, J. B., Carter, G. S., Pratt, L. J., Pearson-Potts, K. A., & Tan, S. Persistent turbulence in the Samoan Passage. Journal of Physical Oceanography, 49(12), (2019): 3179-3197, doi: 10.1175/JPO-D-19-0116.1.
    Description: Abyssal waters forming the lower limb of the global overturning circulation flow through the Samoan Passage and are modified by intense mixing. Thorpe-scale-based estimates of dissipation from moored profilers deployed on top of two sills for 17 months reveal that turbulence is continuously generated in the passage. Overturns were observed in a density band in which the Richardson number was often smaller than ¼, consistent with shear instability occurring at the upper interface of the fast-flowing bottom water layer. The magnitude of dissipation was found to be stable on long time scales from weeks to months. A second array of 12 moored profilers deployed for a shorter duration but profiling at higher frequency was able to resolve variability in dissipation on time scales from days to hours. At some mooring locations, near-inertial and tidal modulation of the dissipation rate was observed. However, the modulation was not spatially coherent across the passage. The magnitude and vertical structure of dissipation from observations at one of the major sills is compared with an idealized 2D numerical simulation that includes a barotropic tidal forcing. Depth-integrated dissipation rates agree between model and observations to within a factor of 3. The tide has a negligible effect on the mean dissipation. These observations reinforce the notion that the Samoan Passage is an important mixing hot spot in the global ocean where waters are being transformed continuously.
    Description: The authors thank Zhongxiang Xao and Jody Klymak, who provided earlier setups of the numerical model, and also Arjun Jagannathan for insightful discussions on the subject of flow over topography. We also thank John Mickett and Eric Boget for their assistance in designing, deploying, and recovering the moorings. In addition, we also thank the crew and scientists aboard the R/V Revelle and R/V Thompson, without whom the data presented in this paper could not have been gathered. Ilker Fer and two anonymous reviewers provided thoughtful feedback that improved the paper. This work was supported by the National Science Foundation under Grants OCE-1029268, OCE-1029483, OCE-1657264, OCE-1657795, OCE-1657870, and OCE-1658027.
    Keywords: Gravity waves ; Turbulence ; Abyssal circulation ; Mixing ; Tides
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  • 39
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2020. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 50(3), (2020): 715-726, doi:10.1175/JPO-D-19-0021.1.
    Description: Closing the overturning circulation of bottom water requires abyssal transformation to lighter densities and upwelling. Where and how buoyancy is gained and water is transported upward remain topics of debate, not least because the available observations generally show downward-increasing turbulence levels in the abyss, apparently implying mean vertical turbulent buoyancy-flux divergence (densification). Here, we synthesize available observations indicating that bottom water is made less dense and upwelled in fracture zone valleys on the flanks of slow-spreading midocean ridges, which cover more than one-half of the seafloor area in some regions. The fracture zones are filled almost completely with water flowing up-valley and gaining buoyancy. Locally, valley water is transformed to lighter densities both in thin boundary layers that are in contact with the seafloor, where the buoyancy flux must vanish to match the no-flux boundary condition, and in thicker layers associated with downward-decreasing turbulence levels below interior maxima associated with hydraulic overflows and critical-layer interactions. Integrated across the valley, the turbulent buoyancy fluxes show maxima near the sidewall crests, consistent with net convergence below, with little sensitivity of this pattern to the vertical structure of the turbulence profiles, which implies that buoyancy flux convergence in the layers with downward-decreasing turbulence levels dominates over the divergence elsewhere, accounting for the net transformation to lighter densities in fracture zone valleys. We conclude that fracture zone topography likely exerts a controlling influence on the transformation and upwelling of bottom water in many areas of the global ocean.
    Description: The data used in this study were collected in the context of several projects funded by the U.S. National Science Foundation (NSF), in particular BBTRE (OCE-9415589 and OCE-9415598) and DoMORE (OCE-1235094). Funding for the analysis was provided as part of the NSF DoMORE and DECIMAL (OCE-1735618) projects. Author Ijichi is a Japan Society for the Promotion of Science (JSPS) Overseas Research Fellow. Comments on an early draft of this paper by Jim Ledwell and Bryan Kaiser, as well as topical discussions with Jörn Callies and Trevor McDougall, are gratefully acknowledged. The paper was greatly improved during the review process, in particular because of the critical comments from one of the two anonymous reviewers.
    Keywords: Diapycnal mixing ; Topographic effects ; Turbulence ; Upwelling/downwelling ; Bottom currents/bottom water
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  • 40
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 47 (2017): 2611-2630, doi:10.1175/JPO-D-16-0259.1.
    Description: This study reports the results of large-eddy simulations of an axisymmetric turbulent buoyant plume in a stratified fluid. The configuration used is an idealized model of the plume generated by a subglacial discharge at the base of a tidewater glacier with an ambient stratification typical of Greenland fjords. The plume is discharged from a round source of various diameters and characteristic stratifications for summer and winter are considered. The classical theory for the integral parameters of a turbulent plume in a homogeneous fluid gives accurate predictions in the weakly stratified lower layer up to the pycnocline, and the plume dynamics are not sensitive to changes in the source diameter. In winter, when the stratification is similar to an idealized two-layer case, turbulent entrainment and generation of internal waves by the plume top are in agreement with the theoretical and numerical results obtained for turbulent jets in a two-layer stratification. In summer, instead, the stratification is more complex and turbulent entrainment by the plume top is significantly reduced. The subsurface layer in summer is characterized by a strong density gradient and the oscillating plume generates internal waves that might serve as an indicator of submerged plumes not penetrating to the surface.
    Description: This work was supported by Linné FLOW Centre at KTH and the Academy of Finland Centre of Excellence program (Grant 307331) (E. E.) and VR Swedish Research Council, Outstanding Young Researcher Award, Grant VR 2014-5001 (L. B.). Support to C. C. was given by the NSF Project OCE-1434041.
    Description: 2018-04-26
    Keywords: Buoyancy ; Internal waves ; Turbulence ; Jets ; Oscillations ; Large eddy simulations
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  • 41
    Publication Date: 2023-02-28
    Description: Author Posting. © American Meteorological Society, 2022. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 52(6), (2022): 1091–1110, https://doi.org/10.1175/JPO-D-21-0068.1.
    Description: Hundreds of full-depth temperature and salinity profiles collected by Deepglider autonomous underwater vehicles (AUVs) in the North Atlantic reveal robust signals in eddy isopycnal vertical displacement and horizontal current throughout the entire water column. In separate glider missions southeast of Bermuda, subsurface-intensified cold, fresh coherent vortices were observed with velocities exceeding 20 cm s−1 at depths greater than 1000 m. With vertical resolution on the order of 20 m or less, these full-depth glider slant profiles newly permit estimation of scaled vertical wavenumber spectra from the barotropic through the 40th baroclinic mode. Geostrophic turbulence theory predictions of spectral slopes associated with the forward enstrophy cascade and proportional to inverse wavenumber cubed generally agree with glider-derived quasi-universal spectra of potential and kinetic energy found at a variety of locations distinguished by a wide range of mean surface eddy kinetic energy. Water-column average spectral estimates merge at high vertical mode number to established descriptions of internal wave spectra. Among glider mission sites, geographic and seasonal variability implicate bottom drag as a mechanism for dissipation, but also the need for more persistent sampling of the deep ocean.
    Description: This work was funded by NSF Grant 1736217 and would not have been possible without the help of Kirk O’Donnell, James Bennett, Noel Pelland, and all contributors to Deepglider development. We additionally thank the captain crew of the R/V Atlantic Explorer and the BATS team at the Bermuda Institute of Ocean Sciences, particularly Rod Johnson, as well as Seakeepers International for their professionalism, capability, and generous assistance in deploying and recovering gliders.
    Keywords: North Atlantic Ocean ; Eddies ; Mesoscale processes ; Turbulence ; Energy transport ; In situ oceanic observations ; Oceanic variability
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  • 42
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 10 (1997), S. 305-310 
    ISSN: 0894-3230
    Keywords: non-covalent interactions ; host-guest complexes ; fluorinated phenyl compounds ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Complexation constants with the macrocyclic azoniacyclophane CP44 and phenyl guest compounds with at least four fluorine atoms or alternatively protons at the ring were obtained by NMR shift titrations in water. The fluorinated compounds show free energies of complexation which are smaller by ΔΔG=3·4-7·7 kJ mol-1 in comparison with the protonated compounds. The NMR shifts induced upon 100% complexation (CIS values) were obtained simultaneously from non-linear least-squares fitting and indicate intra-cavity inclusion in all cases. The CIS values agree roughly with screening constants calculated from aromatic ring current and linear electric field effects, the latter resulting from the permanent charges at the host compound. Molecular mechanics calculations (CHARMm) indicate that intracavity inclusion is possible with all compounds with negligible strain induced (〈1 kJ mol-1) in the macrocycle upon complexation. In contrast, α-cyclodextrin can accommodate fluorinated phenyl compounds only at the rim of the cavity without larger strain. Preliminary data with α-cyclodextrin, obtained by competitive UV-visible titration with methyl orange, indicate again a smaller association free energy (ΔΔG=1·-7 kJ mol-1) for pentafluorphenol compared with normal phenol as guest. © 1997 John Wiley & Sons, Ltd.
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  • 43
    ISSN: 0894-3230
    Keywords: hydrophobic cavity characterization ; cyclophanes ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The guest-binding behavior of two different cyclophane hosts, each being capable of providing a three-dimensionally extended hydrophobic cavity toward aromatic guests, was examined in aqueous media: a steroid cyclophane bearing four rigid cholate moieties and an octopus cyclophane having four flexible double-chain segments. Even though the binding constant for 2,7-dihydroxynaphthalene with the steroid cyclophane was comparable to that with the octopus cyclophane, the guest binding modes were very different from each other, as confirmed by 1H NMR spectroscopy. That is, the steroid cyclophane incorporates the guest into its rigid macrocyclic cavity with axial geometry whereas the octopus cyclophane provides a three-dimensional space created by the macrocyclic skeleton and the flexible hydrocarbon chains so that the long axis of the guest becomes more or less perpendicular to the molecular axis of the host upon complexation. Temperature-dependent molecular recognition by these hosts toward 8-anilinonaphthalene-1-sulfonate was examined by means of fluorescence spectroscopy. Characteristic differences in the guest-binding mode between these hosts were sensitively reflected in the thermodynamic entropy change on host-guest complexation and the temperature-dependent microscopic viscosity experienced by the guest at the binding site. © 1997 John Wiley & Sons, Ltd.
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  • 44
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 10 (1997), S. 254-272 
    ISSN: 0894-3230
    Keywords: π-π interactions ; self-assembly ; catenanes ; cyclophanes ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The recent surge of interest in the control of molecular organization in both the solution state (i.e. self-assembly) and the solid state (i.e. crystal engineering) has led researchers to recognize increasingly the importance of weak non-covalent interactions. The design and synthesis of an efficient molecular construction set are dependent upon a very close interplay between x-ray crystallography and synthetic chemistry. π-π Stacking interactions between π-donors, such as hydroquinone, resorcinol or dioxynaphthalene residues, and π-accepting ring systems, such as bipyridinium or π-extended viologen units, can govern the self-assembly of a variety of complexes and interlocked molecular compounds in both the solid and solution states. Non-covalent bonding interactions (i.e. π-π interactions) can be considered as information vectors: they define and rule the self-assembly processes that lead to the formation of the desired molecular and supramolecular architectures, and thereafter they still govern the dynamic processes occurring within the self-assembled structures and superstructures. The manner in which such molecules and supermolecules can contribute to an understanding of non-covalent interactions at both structural and superstructural levels is described, with reference to numerous examples of self-assembly processes in synthesis, of dynamic processes in the solution state, and of the packing of molecules and molecular complexes in the solid state. © 1997 John Wiley & Sons, Ltd.
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  • 45
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 10 (1997), S. 323-334 
    ISSN: 0894-3230
    Keywords: redox-switched amphiphiles ; ferrocene derivatives ; vesicles ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ---Thirty ferrocene derivatives were prepared and their ability to form vesicles in aqueous solution when oxidized was assessed. The compounds included alkyl ferrocenylmethyl ether derivatives of the form C10H9FeCH2OR in which R=octyl, dodecyl, tetradecyl, hexadecyl, octadecyl and eicosanyl. One single-tailed amine derivative, C10H9FeCH2NR2, R=octadecyl, was studied. Alkylferrocene derivatives had the form C10H9FeR in which R=butyl, decyl, tetradecyl, hexadecyl, octadecyl, eicosanyl and docosanyl. Sixteen symmetrical 1,1′-disubstituted ferrocenes were also studied. Three ethers were of the form C10H8Fe-1,1′-(CH2OR),2, R=tetradecyl, hexadecyl and octadecyl. Four corresponding dialkyl derivatives of the form C10H8Fe-1,1′-R2, R=decyl, tetradecyl, hexadecyl and octadecyl, were assessed. Finally, a range of 1,1′-disubstituted ferrocene derivatives were analyzed. These all had the form C10H8Fe-1,1′-(COR)2, for which R has the following identities: octyl, tridecyl, pentadecyl and heptadecyl (ketones); heptadecyloxy, 3-cholesteryl and 3-cholestanyl (esters); and two amides, R=NHC18H37 and N(C18H37)2. The alkyl and ether derivatives could be readily oxidized and formed vesicular aggregates upon sonication. The ketones, esters and amides could be oxidized but the ferricenium derivatives did not form stable aggregates. An interesting observation is that the aggregates formed were vesicular whether the ferrocene derivative had one or two alkyl tails. © 1997 John Wiley & Sons, Ltd.
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  • 46
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    Journal of Physical Organic Chemistry 10 (1997), S. 273-285 
    ISSN: 0894-3230
    Keywords: cation-π interactions ; calix[n]arenes ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Non-covalent intermolecular forces have been recognized as a very important part of molecular interactions in complex biological systems. The fundamental functions of living matter such as transcription of genetic information in DNA, spatial arrangement of protein molecules, enzymatic functions or immunity system response are enabled owing to the presence of weak non-covalent forces based on hydrogen bonding interactions, van der Waals interactions, electrostatic interactions, hydrophobic effects, etc. Recently, among them so-called "cation-π" interactions have been proved to contribute to the overall binding process in various artificial or biological systems. Calix[n]arenes have emerged as an important family of molecules with promising applications in many branches of chemistry. Because of their suitable molecular preorganization with aromatic units being "concentrated' in a relatively small space, calix[n]arenes represent interesting compounds exhibiting an enhanced ability for cation-π interactions. The importance of such forces in calix[n]arene chemistry is demonstrated here on several recent examples. © 1997 John Wiley & Sons, Ltd.
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  • 47
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    Journal of Physical Organic Chemistry 10 (1997), S. 335-342 
    ISSN: 0894-3230
    Keywords: hydrophobic interactions ; aqueous solutions ; living systems ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ---Evidence is provided for the enormous role of hydrophobic interactions in aqueous solutions. It is concluded that complementary functions of hydrophilic and of hydrophobic species are in continuous operation and that these are a conditio sine qua non for the existence of the liquid. With regard to the supermolecular aggregations, hydrophobic interactions are operative on the highest hierarchic levels of the system organization, i.e. at the interface and at the holes around dissolved hydrophobic species. It is further emphasized that water is essential both for the unity and for the differentiation of each living organism. With regard to its role for the differentiation of the body, the hydrophobic interactions are of paramount importance, notably those provided by amphipathic solutes. The cell membrane is considered to be the result of interactions between the highest hierarchic levels of intracellular and extracellular water. The hydrophobic double layer provides the barriers for the separation of intracellular and extracellular water and at the same time the connections for recognition and for exchange of information between them. The DNA structures obtain conservative boundary conditions for their surrounding water systems which do not freeze at -60 °C. These water systems are dynamically superior to all other parts of the water system of the organism. It is suggested that more knowledge about the abilities of liquid water can be obtained by giving appropriate attention to its properties within the living body. © 1997 John Wiley & Sons, Ltd.
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  • 48
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    Journal of Physical Organic Chemistry 10 (1997), S. 343-346 
    ISSN: 0894-3230
    Keywords: charge-transfer complexes ; intrinsic (gas-phase) basicities ; stability ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ---The standard Gibbs energy changes for the formation of 1:1 charge-transfer complexes between molecular iodine and several bases in solution at 25·0 °C [ΔG0l2(soln)] were determined experimentally. The bases were 2,2,2-trifluoro- ethylamine, cyclopropylamine and 1,1,3,3-tetramethylguanidine. These [ΔG0l2(soln)] values, determined in n-heptane, and also that for the formation of the 1:1 complex between 2,2,2-trifluoroethanethiol and molecular iodine in dichloromethane, were found to follow with excellent precision the correlation equations linking ΔG0l2(soln) and the intrinsic (gas-phase) basicities of N(sp3), N(sp2) and S(sp3) bases. These findings strongly support previous conclusions regarding the relationship between gas-phase and solution reactivity data. © 1997 John Wiley & Sons, Ltd.
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  • 49
    ISSN: 0894-3230
    Keywords: molecular recognition ; non-aqueous titration ; hydrogen bonding ; proton transfer ; pKa shifts ; acid-base catalysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Whenever hydrogen bonding is involved in molecular recognition, the possibility of a proton transfer from the donor to the acceptor arises. In most cases the pKa of the donor is far enough above the pKa of the conjugate acid of the acceptor for it to be clear that no proton transfer will occur. However, as the difference between the donor and acceptor pKas decreases, it can become difficult to predict whether a proton transfer will occur. Since most hydrogen bond-driven molecular recognition is studied in low dielectric solvents, non-aqueous titrations can be used to measure the pKas and therefore predict proton transfers. In this paper three studies which involved non-aqueous titrations are summarized. The first deals with distinguishing simple proton transfer from host-guest complex formation. The second involves measuring pKa shifts upon host-guest complex formation. The last is a study of the catalysis of a phosphoryl transfer. In all three scenarios the non-aqueous titration method gave results which would have been difficult to obtain by other means, and which proved crucial for a complete understanding of the molecular recognition process. © 1997 John Wiley & Sons, Ltd.
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  • 50
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    Journal of Physical Organic Chemistry 10 (1997), S. 347-350 
    ISSN: 0894-3230
    Keywords: benzene · · · hexafluorobenzene ; supramolecular synthon ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The benzene · · · hexafluorobenzene stacking interaction was evaluated at several levels of theory. At the MP2/6-31G** level, it is estimated that the interaction is stabilizing by approximately 3.7 kcal mol-1. Lower levels of theory perform poorly on this system. This is a fairly strong non-covalent interaction, suggesting this motif may be a valuable supramolecular synthon. © 1997 John Wiley & Sons, Ltd.
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  • 51
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    Journal of Physical Organic Chemistry 10 (1997), S. 358-368 
    ISSN: 0894-3230
    Keywords: hydrogen bonding ; RP-HPLC C18 stationary phases ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The linear free energy equationlogk′ = c + rR2 + sπ2H + a∑α2H + b∑β2 + vVxwas applied to the capacity factors for various sets of solutes on C18 stationary phases with aqueous methanol and acetonitrile eluents. Here, k′ are the capacity factors for a series of solutes with a given C18 phase and a given eluent, and R2, π2H, ∑α2H, ∑β2, Vx are parameters or descriptors of the solutes as follows: R2 is an excess molar refraction, π2H is the solute polarizability/dipolarity, ∑α2H and ∑β2 are the solute hydrogen-bond acidity and basicity and Vx is the solute volume. It is shown that although the regression coefficients r, s, a, b and v vary widely within the C18 column and mobile phase used, the ratios r/v, s/v, a/v and b/v are remarkably constant. Thus, for the retention of 25 series of solutes on six different C18 columns with 30-90% aqueous methanol as the eluent, all the 25 LFER equations can be combined into one general equation:logk′ = c + v(0.13 R2 - 0.32 π2H - 0.22 ∑α2H - 0.90 ∑β2O + 1.00 Vx)where only c and v vary from system to system. For 11 other phases for which data are available, the ratios v/A and (v + c)/A are constant, where A is the quantity of stationary phase per unit surface area. Similar results were found with C18 phases and aqueous acetonitrile as eluents. Although a first examination of equations based on the first equation above suggests that various C18 phases behave differently, for example the v coefficient, that is related to the observed hydrophobicity of a stationary phase relative to the mobile phase, varies considerably from phase to phase with the same eluent, a detailed analysis led to the conclusion that all the C18 phases examined have roughly the same hydrophobicity, when the v coefficients are corrected for the quantity of stationary phase per unit surface area. It is suggested that these corrected v coefficients, v/A and (v + c)/A, can be regarded as the ‘intrinsic’ phase hydrophobicity. © 1997 John Wiley & Sons, Ltd.
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  • 52
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    Journal of Physical Organic Chemistry 10 (1997), S. 286-291 
    ISSN: 0894-3230
    Keywords: chiral recognition ; cyclodextrins ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ---The mechanisms for chiral recognition by cyclodextrins (CDxs) are discussed. Examples of host-guest systems where the "lock-and-key mechanism" and the "three-point rule" are applicable are cited and discussed. Most results reported so far suggest that the ability of native CDxs and chemically modified CDxs to discriminate between enantiomers of guests having a central chirality is low in aqueous solutions. Small ΔΔG values for enantioselective complexation of CDxs with amino acids seem to be due to unpredictably small changes in the structures of the complexes of the guest enantiomers. Therefore, it is very difficult to prove the participation of hydrogen bonding in chiral recognition through the "three-point rule" in these systems. The use of the Coulomb interaction and the coordinate bonds as point interactions is discussed. CDxs might be good hosts to recognize axial chirality or helicity of guests. Hydrogen bonding in water is assumed in the recognition of the helicity of bilirubin. Very large ΔΔG values have been reported for the chiral recognition of the binaphthyl derivatives. Such a system seems to be a suitable model system to study the mechanism of chiral recognition by CDxs. © 1997 John Wiley & Sons, Ltd.
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  • 53
    ISSN: 0894-3230
    Keywords: Menschutkin reaction ; duality of SN1, SN2 mechanisms ; benzyl tosylates ; Yukawa-Tsuno equation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate data for the Menschutkin reaction between strongly activated Z-substituted benzyl p-toluenesulfonates and Y-substituted N,N-dimethylanilines in acetonitrile at 35 °C fit the equation, kobs  =  k1 + k2 [DMA], which is consistent with concurrent first- and second-order processes. The k1 and k2 values for each substrate were separated based on the above equation. The SN1 rate constant, k1, is unaffected by the nature of the nucleophile, whereas the SN2 rate constant, k2, increased with the electron-donating substituent of the N,N-dimethylaniline. The substituent effect on the k1 values is linearly correlated by the Yukawa-Tsuno equation with ρ  =  -5.2 and r  =  1.3. The unimolecular reaction can be regarded as a classical SN1 mechanism. In contrast, that on the k2 values shows an upward curvature when analyzed by the Brown σ+ treatment. These results are ascribed to the simultaneous and independent occurrence of SN1 and SN2 mechanisms in the present Menschutkin reaction. © 1998 John Wiley & Sons, Ltd.
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  • 54
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    Journal of Physical Organic Chemistry 11 (1998), S. 231-231 
    ISSN: 0894-3230
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No Abstract
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  • 55
    ISSN: 0894-3230
    Keywords: calorimetry ; IR spectra ; ketones ; solvation ; Chemistry ; Theoretical, Physical and Computational Chemistry
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Solution enthalpies of n-hexane, acetone, butan-2-one and octan-2-one in a series of tetrachloromethane-acetonitrile mixtures and the carbonyl stretching absorption frequencies in the IR spectra of these ketones were determined. It was found that over the whole range of concentrations (varying from neat tetrachloromethane up to neat acetonitrile) the solvation enthalpy of these compounds can be obtained additively from the contributions of the alkyl and carbonyl fragments. The solvent effect on the solvation enthalpy of the carbonyl group was found to be satisfactorily correlated with the corresponding IR frequency shifts of the C=O group. It was also found that the sensitivities of the carbonyl IR frequencies to the solvent composition are different for various ketones. From both IR and calorimetric data, the preferential solvation parameters were evaluated. The differences between the IR spectroscopic and calorimetric data are discussed. © 1998 John Wiley & Sons, Ltd.
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  • 56
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    Journal of Physical Organic Chemistry 11 (1998), S. 261-272 
    ISSN: 0894-3230
    Keywords: 1-substituted 2-pyrrolidinones ; C=O stretching frequencies ; solvent effects ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In an effort to model solute-solvent interactions, the C=O stretching frequencies of five 1-substituted 2-pyrrolidinones and four other carbonyl-containing compounds were measured for 30 common solvents. These were then correlated with four empirical parameter sets and one theoretical (computational) parameter set. While an empirical parameter set gave the best correlation equations, the theoretical parameter equations are physically and statistically significant. Solvent volume, polarizability and hydrogen bond donor acidity (capacity) terms are significant in the correlation equations. © 1998 John Wiley & Sons, Ltd.
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  • 57
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    Journal of Physical Organic Chemistry 11 (1998), S. 232-240 
    ISSN: 0894-3230
    Keywords: P - S bond cleavage ; hydroperoxidolysis ; nerve agent VX ; molecular orbital calculations ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The P - S bond cleavage process in the hydroperoxidolysis of a model system for the nerve agent VX was studied using ab initio and semiempirical molecular orbital methods. Aqueous solvation effects were included through single-point calculations using the semiempirical SM5.2PD/A continuum solvation model and geometries optimized at the HF/MIDI! level of theory. The predominant pathway for P - S bond cleavage involves pseudorotation of a low-energy trigonal bipyramidal intermediate followed by apical ligand ejection. In aqueous solution, the free energy barriers for these processes are found to be 14.3 and 4.6 kcal mol-1, respectively, with electronic energies calculated at the MP2/cc-pVDZ//HF/MIDI! level of theory. By comparison with another continuum model of solvation (PCM), it is concluded that the SM5.2PD/A model performs well even for hypervalent phosphorus species, in spite of not having included any such molecules in the model's parameterization set. © 1998 John Wiley & Sons, Ltd.
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  • 58
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    Journal of Physical Organic Chemistry 11 (1998), S. 407-410 
    ISSN: 0894-3230
    Keywords: gas-phase thermolysis ; N-methyl-N-phenyl-tert-butylsulfenamide ; morpholinyl-tert-butylsulfenamide ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: N-Methyl-N-phenyl-tert-butylsulfenamide (MPSA) and morpholinyl-tert-butylsulfenamide (MOSA) were thermolyzed in a stirred-flow reactor at temperatures of 340-390 °C and pressures of 7-13 Torr, using toluene as carrier gas, at residence times of 0.3-1.3 s. Isobutene was formed in 99% yield through first-order reactions having the following Arrhenius parameters (A,s-1, Ea, kJ mol-1): MPSA, log A  =  12.41 ± 0.02, Ea  =  158.8 ± 0.2; MOSA, log A  =  12.91 ± 0.22, Ea  =  159 ± 3. It is proposed that the elimination of isobutene takes place by unimolecular reaction mechanisms involving polar, four-center cyclic transition states, forming S-unsubstituted thiohydroxylamines as co-products. Thermochemical parameters, estimated by semiempirical AM1 calculations, are reported for the latter and for the parent molecules. © 1998 John Wiley & Sons, Ltd.
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  • 59
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    Journal of Physical Organic Chemistry 11 (1998), S. 411-418 
    ISSN: 0894-3230
    Keywords: 2,2′-bisbenzimidazolyl ; tautomerism ; NMR ; semi-empirical calculations ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A dynamic NMR study of the tautomerism of 2,2′-bisbenzimidazolyl in DMSO-d6 and a mechanistic interpretation of the process, based on a stepwise, single-proton transfer and formation of a zwitterionic intermediate, are presented. This interpretation is substantiated by semi-empirical calculations of the postulated intermediate and transition state, that yield results which are compared with previous studies on related aliphatic systems. © 1998 John Wiley & Sons, Ltd.
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  • 60
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    Journal of Physical Organic Chemistry 11 (1998), S. 397-406 
    ISSN: 0894-3230
    Keywords: bond dissociation energy ; acidity ; phenylsulfenylamides ; phenylsulfenylanilides ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Acidities and bond dissociation energies (BDEs) of the N-H bond in two phenylsulfenylamides, PhSNHBz and PhSNH-t-Bu, and four phenylsulfenylanilides, 4-GC6H4NHSPh, where G  =  MeO, H, Br and CN, were measured in order to compare the effects of substituents on acidities and BDEs of N - H bonds with those of C - H bonds. The effects of PhS groups on acidities and BDEs in a series of C - H acids were found to be comparable to those on acidities and BDEs of PhS in a similar series of N - H acids. Comparisons were also made of the effects of changing the oxidation state of sulfur in the series PhS, PhSO and PhSO2 on the acidities and BDEs of adjacent N - H and C - H bonds in weak acids. Hammett-type plots of pKHA values for phenyl benzyl sulfones (4-GC6H4CH2SO2Ph) and phenylsulfenylanilides (4-GC6H4NHSPh) were linear vs σp- values. A linear plot was obtained and explained for a plot of BDE of the N - H bonds in remotely substituted phenylsulfonylanilides with σ+ values. Plots of BDEs vs Eox(A-) were also linear for 4-substituted phenylsulfenylanilides (4-GC6H4NHSPh), phenylsulfonylanilides (4-GC6H4NHSO2Ph) and phenyl benzyl sulfones (4-GC6H4CH2SO2Ph). © 1998 John Wiley & Sons, Ltd.
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  • 61
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    Journal of Physical Organic Chemistry 11 (1998), S. 387-391 
    ISSN: 0894-3230
    Keywords: α-diamides ; 17O NMR ; conformation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 17O NMR spectra of several α-diamides were obtained at natural isotopic abundance in acetonitrile solution in order to study the conformations of these compounds in solution. The 17O NMR shifts vary with the intercarbonyl dihedral angle α in a sense opposite to that observed for α-diketones. © 1998 John Wiley & Sons, Ltd.
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  • 62
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    Journal of Physical Organic Chemistry 11 (1998), S. 392-396 
    ISSN: 0894-3230
    Keywords: 8-azaadenine ; tautomerism ; theoretical study ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The prototropic tautomerism of 8-azaadenine (azaade) was studied theoretically by means of ab initio methods, in both the gas phase and aqueous solution. A number of tautomeric forms were not included in the calculations after applying a stepwise elimination procedure based on both AM1 and HF/6-31G* energy values. The tautomers 9H-azaade, 8H-azaade and 7H-azaade survived to this elimination and their optimized geometries and energies were calculated at the MP2/6-31*//HF/6-31G* level. To include the solvent effects, two self-consistent reaction field method were used: (1) Onsager's SCRF with multipolar expansion up to the hexadecapolar term and (2) the isodensity polarizable continuum method (IPCM). Both methods produce similar results, although the latter represents better the situation in aqueous solution. The stability order in solution, 8H- 〉 9H- 〉 7H-azaade, differs slightly from that found in the gas phase, implying that in general the electrostatic effects in solution are important, but the intrinsic stability of these species in the gas phase overcomes the solvent effect. © 1998 John Wiley & Sons, Ltd.
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  • 63
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    Journal of Physical Organic Chemistry 11 (1998), S. 377-377 
    ISSN: 0894-3230
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No abstract.
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  • 64
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    Journal of Physical Organic Chemistry 11 (1998), S. 419-425 
    ISSN: 0894-3230
    Keywords: 5-nitro-5′-dimethylamino-2,2′-bisthiophene ; π* probe dye ; cyclic voltammetry ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cyclic voltamograms of the solvatochromic dye 5-nitro-5′-dimethylamino-2,2′-bisthiophene (1), introduced recently as a sensitive π* probe, were recorded in different solvents. An EPR spectrum of the anionic radical of 1 in DMSO was obtained and compared with other spectra of analogous substituted bisthiophene radicals. It was found that the presence of a donor- acceptor pair of substituents in 1-⋅ reduces significantly the rotational barrier of the radical compared with the unsubstituted bithienyl radical anion 2-⋅. This is the result of an electronic repulsion between the donor ring fragment and the added electron in the coplanar radical, which does not exist in 2-⋅. © 1998 John Wiley & Sons, Ltd.
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  • 65
    ISSN: 0894-3230
    Keywords: calix[4]resorcinarenes ; organophosphorus compounds ; solvatophobic interactions ; host-guest complexation ; high-performance liquid chromatography ; x-ray analysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reversed-phase high-performance liquid chromatography [LiChrosorb RP-18,UV detection at 254 nm and acetonitrile-water (86:14,v/v) as mobile phase] was applied to studies of the host-guest complexation of tetraalkylcalix[4]resorcinareneoctols and their upper rim phosphoryl, sulfonyl and dialkylaminomethyl derivatives with some aromatic guests in the mobile phase. It was shown that the formation of the inclusion complexes results in changes in the retention of aromatic guests and improves their separation. Stability constants of the complexes were calculated from the dependences of the l/k′ values of the aromatic guest on the concentration of the calix[4]resorcinarene in the mobile phase. The molecular structure of 4,6,16,18-tetrahydroxy-10,12,22,24-tetrakis(dipropoxyphosphoryloxy)-2,8,14,20-tetramethylcalix[4]resorcinarene (12) was determined. Crystal data for 12 are P21/n, a  =  16.708(9) Å, b  =  18.683(6) Å, c  =  20.243(5) Å, β  =  95.75(3)°, V  =  6287(4) Å3 and Z  =  4. Compound 12 exists in a boat conformation, in which two opposite unsubstituted resorcinol rings of the macrocyclic skeleton lie in the plane formed by four methine bridges and two diphosphorylated rings are perpendicular to the plane. © 1998 John Wiley & Sons, Ltd.
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  • 66
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    Journal of Physical Organic Chemistry 11 (1998), S. 378-386 
    ISSN: 0894-3230
    Keywords: alkylboronic acids ; arylboronic acids ; ab initio ; MM3 ; molecular mechanics ; force field parameters ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The boronic acid functional group has been incorporated into various biologically important compounds. In order to study this class of compounds better with molecular mechanics, five alkyl- and arylboronic acids were calculated using ab initio methods (Spartan) at the RHF/6-31G* level. MM3 force field parameters were developed based on the theoretically calculated geometries, vibrational spectra, and torsional profiles. © 1998 John Wiley & Sons, Ltd.
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  • 67
    ISSN: 0894-3230
    Keywords: γ-lactones ; base-catalysed hydrolysis ; reactivity-structure correlations ; isobenzofuranones ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rate coefficients were measured for the base-catalysed hydrolysis of a series of substituted 3-(phenoxy- or thiophenoxymethylene)-(Z)-1(3H)-isobenzfuranones (3-phenoxy- or thiophenoxymethylenephthalides) in 70% (v/v) aqueous dioxane at 30.0 °C, in addition to the carbonyl stretching frequencies in chloroform and tetrachloromethane following deconvolution and band separation, when required. The Hammett reaction constants for the alkaline hydrolysis of the 3-/4-substituted phenoxy and thiophenoxy series are ca 0.75 and 1.10, respectively. These results are related to electrostatic field and resonance effects. Successful correlations between the carbonyl stretching frequencies and substituent constants and the rates of alkaline hydrolysis were found. Computational studies using the semi-empirical AM1 method correctly model both the details of the mechanistic pathway and the substituent effects. © 1998 John Wiley & Sons, Ltd.
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  • 68
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    Journal of Physical Organic Chemistry 11 (1998), S. 437-447 
    ISSN: 0894-3230
    Keywords: inductive constants ; theoretical estimation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new model of the inductive effect is proposed, allowing highly accurate theoretical calculations of inductive constants for a diversity of substituents, using a simple and readily available system of mathematics. According to this approach, the inductive effect of a substituent is considered in terms of the additive influence of its constituent atoms. A constant inherent capacity for inductive interaction with a reactive center (with a four-coordinate carbon atom chosen for such a center), represented by an atomic constant σA, is ascribed to each atom. Values of σA for a wide variety of atoms are determined, and their physical meaning is revealed to elucidate to a certain extent the physical nature of the inductive effect. In addition, the proposed model permits the convenient use in calculations of group constants σG characterizing the inductive power of groups. Values of σG are determined for molecular fragments that are most widely dealt with in organic chemistry, and the use of σA or σG constants and of their superposition is shown to have, in most cases, little or no effect on the accuracy and reproducibility of the results obtained. It is also shown that, in terms of the developed approach, the inductive effect of a substituent is closely associated with its conformation. Theoretical inductive constants were calculated for 427 organic, aromatic, organometallic and charged substituents, and they showed perfect correlation with the corresponding experimental values. © 1998 John Wiley & Sons, Ltd.
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  • 69
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    Journal of Physical Organic Chemistry 11 (1998), S. 448-454 
    ISSN: 0894-3230
    Keywords: mandelic acid ; alkaline permanganate ; oxidation ; kinetics ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the oxidation of mandelic acid (MA) by permanganate in aqueous alkaline medium at a constant ionic strength of 1.0 mol dm-3 were studied spectrophotometrically. The reaction shows first-order kinetics in [permanganate ion] and fractional order dependences in [MA] and [alkali]. Addition of products, manganate and aldehyde have no significant effect on the reaction rate. An increase in ionic strength and a decrease in dielectric constant of the medium increase the rate. The oxidation process in alkaline medium under the conditions employed in the present investigation proceeds first by formation of an alkali permanganate complex, which combines with mandelic acid to form another complex. The latter decomposes slowly followed by a fast reaction between the free radical of mandelic acid and another molecule of permanganate to give products. The reaction constants involved in the mechanism were derived. There is good agreement between the observed and calculated rate constants under different experimental conditions. The reaction was studied at different temperatures and activation parameters were computed with respect to the slow step of the proposed mechanism. © 1998 John Wiley & Sons, Ltd.
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  • 70
    ISSN: 0894-3230
    Keywords: Selective arylation ; exocyclic N-position ; 2-pyrimidylnitrenium ion ; tetrazolo[1,5a]pyrimidine ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photo-reactions of tetrazolo[1,5-a]pyrimidine (1) with benzene (2a) and substituted benzenes (2b-f) in the presence of trifluoroacetic acid (TFA) gave 2-(2-, 3- and 4-substituted anilino)pyrimidines (3-5) together with 2-aminopyridine (6) and biphenyl (7) or diarylmethanes (8b, 8c and 8e). From the effect of heavy-atom solvent on the reactions, it is reasonable to assume that 3-5 are formed via a singlet species, but 6-8 via a triplet species. The intermediacy of 2-pyrimidylnitrenium ion is consistent with the evidence derived by the above effect, by a Hammett plot with ρ = -2.9 and by effects of solvent nucleophilicity and counter-anions. The selective exocyclic N-arylation giving 3-5 is discussed. © 1998 John Wiley & Sons, Ltd.
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  • 71
    ISSN: 0894-3230
    Keywords: aryliminodimagnesium ; condensation with NO2 and CO groups ; addition to CN group ; single electron transfer efficiency ; σ-complexation ability ; inter- and intramolecular competition ; bifunctional substrates ; positional effect of functional groups ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ---The reactions of aryliminodimagnesium [ArN(MgBr)2, IDMg] with p′-substituted p-cyanobenzophenones, 1-cyano-9-fluorenone, o-, m- and p-dicyanobenzenes and o-, m- and p-nitrobenzonitriles were examined, and the relative yields of products were referred to the previous results of electron spin resonance studies. The products of condensation with carbonyl and nitro groups and of addition to cyano groups were formed. From the variations of the yields caused by the molar ratio of the magnesium reagent versus substrates and by the substituents of both reactants, the preferred groups were determined. The groups of p- and m-substrates are consistent with the position of highest density of free electrons in the anion radicals, whereas those of the o-substrates are inconsistent. The consistency indicates competition of functional groups reflecting the relative ability of single electron acceptance from the reagent, whereas the inconsistency is ascribed to cooperation of neighbouring groups for σ-complexation with the Mg atom of the reagent. The categories of competition and cooperation are discussed in relation to fundamental features and general governing factors proposed for the IDMg reactions of monofunctional substrates. © 1997 John Wiley & Sons, Ltd.
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  • 72
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    Journal of Physical Organic Chemistry 10 (1997), S. 383-395 
    ISSN: 0894-3230
    Keywords: hydrogen bond strength ; organic groups ; isotopic substitution ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Although the electronic contribution to the strength of a H-bond is unaffected by isotopic substitution, the heavier mass of deuterium compared with protium lowers some of the vibrational frequencies in the complex. The binding energy of the complex, which includes zero-point and thermal vibrational energies, can thus be altered by several tenths of a kcal mol-1 by H/D substitution. Ab initio calculations are used to analyze this phenomenon in a number of common organic functional groups that are prone to form H-bonds: hydroxyl, carboxyl and amide, both self-complexing as homodimers and with water molecules as partners. It is found that any site of D-substitution increases the complexation energy; however, the bridging sites show a stronger preference for D over H than do the non-bridging, or terminal, sites. Hence D-bonding can be considered to be stronger than H-bonding in these functional groups. Of the groups considered, the energetic preference for D over H is greater in the hydroxyl group, so deuterium would be expected to gravitate toward solvent water molecules in isotopic scrambling experiments. The increments in H-bonding energy resulting from each site of substitution are addititve in cases of multiple substitution. © 1997 John Wiley & Sons, Ltd.
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  • 73
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    Journal of Physical Organic Chemistry 10 (1997), S. 253-253 
    ISSN: 0894-3230
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
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  • 74
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    Journal of Physical Organic Chemistry 10 (1997), S. 405-413 
    ISSN: 0894-3230
    Keywords: non-covalent interactions ; thermodynamic hydrogen bond parameter ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ---This paper describes how empirical free energy and/or enthalpy values for hydrogen binding strength are derived from thousands of corresponding measurements between H-bond donors and acceptors, mostly in carbon tetrachloride, and how they can be used to construct common scales or factor values (increments) also for other reactions involving electron donor and acceptor ability of functions. The corresponding databases and programs (HYBOT) allow one to predict thermodynamic values for experimentally unknown equilibria, including also ionophore complexes with crown ethers or cryptands. Applications in QSAR involve the prediction of lipophilicity from any structure on the basis of only two variables, e.g. 234 systems are described this way with a correlation coefficient r=0·96. Similarly, permeabilities and some biological properties such as narcotic activities of chemicals and anti-HIV-1 activity of some porphyrins are evaluated. © 1997 John Wiley & Sons, Ltd.
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  • 75
    ISSN: 0894-3230
    Keywords: inclusion complexation ; cyclobis (paraquat-p-phenylene) ; cyclophanes ; substituted aromatics ; cooperative non-covalent cavity ; external interactions ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ---The cooperative nature of non-covalent interactions which give rise to inclusion complexes involving cyclobis(paraquat-p-phenylene), 14+, and related cyclophane derivatives, 24+-44+, with substituted 1,4-phenyl and 4,4′-biphenyl guests has been studied by spectroscopic techniques and ab initio and semiempirical molecular orbital methods. Inclusion complex formation and stability are primarily determined by the combination of two main interaction modes involving aromatic stacking of the guest within the cyclophane cavity and external interactions between guest side arms and the exterior of the cyclophane. A balance between cavity and external forces results in supramolecular association and is shown to change depending upon the functionality and substitution of the guest. Cavity binding was probed using 1,4-phenyl and 4,4′-biphenyl guests, where for the 1,4-phenyl guests the primary basis for energy stabilization with 14+ is found to be short-range stabilizing electrostatic forces complemented by small amounts of polarizability and charge-transfer. In contrast, the cavity binding between substituted 4,4′-biphenyl guests and 14+ is determined by almost equal contributions of polarizability and electrostatics. The effect of solvent is shown to have only a small effect on the computed geometry of 14+ complexes, but its impact upon binding energies is substantial. The first solvation shell of the cyclophanes is computationally approximated by 12 acetonitriles and satisfies the requirements of the 16 relatively acidic protons on the bipyridinium groups. Good correlations between the computed (with solv ation) and experimental 14+ binding energies are found. The degree of linear correlation improves substantially when the comparison between computed and experimentally observed binding energies is restricted to structurally similar (number of aromatic rings, number of substituents and position of substitution) molecular guests. Furthermore, computed molecular properties, such as polarizability, maximum hardness, softness and electronegativity of the isolated guests, correlate well with 14+ binding energies based upon the same requirement of guest similarity. The non-covalent forces associated with the external cyclophane interactions were studied with guest molecules built from symmetrical 1,4-extensions of hydroquinone composed of aliphatic or ethyleneoxy side arms. In particular, side arm length and functionality, and the position and type of heteroatoms along the chain, were systematically varied to define the external interactions between the guest side arms and different host cyclophanes. Specifically, the ethyleneoxy linkages are shown to provide a large chelate and cooperative effect which direct the binding with 14+. In order to probe further the special geometric and electronic character of 14+, we have synthesized and tested a new supramolecular host, 24+, similar to 14+ but where a pentacycloundecane unit replaces one of the xylyl groups. Both experimental and computed data on the new host emphasize the ideal geometry and electronic nature of the 14+ molecular receptor for aromatic guests. The inclusion complexes discussed in this paper are important not only because they, or similar entities, are the main components of many rotaxanes, catenanes and other switchable molecules, but because the intermolecular interactions involved, such as electrostatics, polarizability and charge-transfer, are ubiquitous in supramolecular chemistry. The information reported on the specific interactions involving the 14+-44+ molecular receptors with substituted aromatic guests can also be extended by analogy to many systems of broad interest. © 1997 John Wiley & Sons, Ltd.
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  • 76
    ISSN: 0894-3230
    Keywords: 3-methyl-2, 4-diphenyl-3-azabicyclo[3.3.1]nonan-9α-ol esters ; analgesics ; synthesis ; structure ; conformation ; pharmacological assays ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of esters derived from 3-methyl-2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9α-ol (1) was synthesized and studied by 1H and 13C NMR spectroscopy, and the crystal structure of 3-methyl-2,4-diphenyl-9α-(3,5-dimethylbenzoyloxy)-3-azabicyclo[3.3.1]nonane (2) was determined by x-ray diffraction. The compounds studied display in CDCl3 a preferred flattened chair-chair conformation. This bicycle conformation is similar to that found for 2 in the crystal state. Pharmacological assays on mice were performed to evaluate drug-induced behavioral alteration, peripheral or central acute toxicity and analgesic activity. © 1998 John Wiley & Sons, Ltd.
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  • 77
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    Journal of Physical Organic Chemistry 11 (1998), S. 101-108 
    ISSN: 0894-3230
    Keywords: encounter complexes ; 1-cyanonaphthalene ; norbornadiene ; stereospecific ; nucleophilic trapping ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photo-induced electron donor-acceptor reactions between 1-cyanonaphthalene (CNN) and norbornadiene (N) generate products of several structure types. Methanol adducts (1-3) formed in polar solvents are rationalized via the radical cation, N+·, and stereospecific (exo-) nucleophilic attack by methanol. In less polar solvents, CNN and N form [2 + 2]-cycloadducts, exclusively on the exo-face of N. In non-polar solvents containing methanol, CNN, N and methanol combine to form 1:1:1 adducts, containing the sensitizer on the endo- and the methoxy groups on the exo-face. The formation of these products is rationalized via the trapping of encounter complexes of different geometries. Any rearrangement of the norbornenyl system can be eliminated, since neither tricyclyl nor 7-methoxynorbornenyl structures are formed. Apparently, the alcohol captures an endo-encounter complex of CNN and N by attack from the exo-face, similar to the attack of methanol on N+·. © 1998 John Wiley & Sons, Ltd.
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  • 78
    ISSN: 0894-3230
    Keywords: aromaticity ; Diels-Alder transition states ; Diels-Alder adducts ; reaction mechanism ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Semiempirical, ab initio and DFT investigations on the mechanism of the Diels-Alder reactions of a set of masked dienes (ring-fused dienes), viz. o-quinodimethane, anthracene and α-vinylnaphthalene, with ethylene, and reactions of α-vinylnaphthalene with maleic anhydride and p-benzoquinone were performed with a view to understanding the role of masking factors on the activation and reaction energies. The reactions were found to occur in a concerted fashion through synchronous transition states (TSs) in the first two reactions and through asynchronous TS in the other case. Of the compounds studied, o-quinodimethane is the most reactive diene both in a kinetic and a thermodynamic sense. α-Vinylnaphthalene reacts faster with maleic anhydride than p-benzoquinone, as expected, and two possible stereoselective TSs, one endo and the other exo, have been located for the reactions of α-vinylnaphthalene with the above dienophiles. Calculations show that the relative gain or loss of aromatic stabilization of the benzonoid ring in the transition state and in the product seems to play a major role in the kinetic and thermodynamic control of these reactions. © 1998 John Wiley & Sons, Ltd.
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  • 79
    ISSN: 0894-3230
    Keywords: methylbenzoic acids ; infrared spectra ; conformation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Infrared spectra of all isomers of polymethyl-substituted benzoic acids were recorded in the carbonyl and hydroxyl regions in tetrachloromethane at various concentrations and interpreted in terms of conformation. According to a plot of ν(C=O) of the monomeric form vs Hammett substituent constants σ, these compounds may be classified into two classes. Derivatives with none or only one methyl group in the ortho position are concluded to exist in an equilibrium of two planar conformations, unless the equilibrium is degenerate. Derivatives with two ortho-situated methyl groups are concluded to take up one non-planar conformation. These findings are supported by the shape of the hydroxyl and carbonyl bands, which are unsymmetrical in the former class, although they could not be reliably separated into bands pertinent to the individual conformers. This conclusion is at variance with the common interpretation which has invariably ascribed to these and similar ortho derivatives non-planar conformations with a variable torsional angle. © 1998 John Wiley & Sons, Ltd.
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  • 80
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    Journal of Physical Organic Chemistry 11 (1998), S. 149-154 
    ISSN: 0894-3230
    Keywords: P - C bond cleavage ; phosphoranyl radicals ; organophosphonate biodegradation ; ab initio calculations ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Barrier heights for P - C bond homolysis in P-hydroxy-P-methyl-P,P-dioxophosphoranyl and P,P,P-trihydroxy-P-methylphosphoranyl were calculated using well correlated levels of electronic structure theory. The best estimate for the difference in barriers between the two indicates that homolysis is more facile for P,P,P-trihydroxy-P-methylphosphoranyl by roughly 9 kcal mol-1. This result suggests that bacterial pathways leading to P - C bond cleavage in organophosphonate derivatives will preferentially proceed via initial one-electron reduction of substrates rather than oxidation. © 1998 John Wiley & Sons, Ltd.
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  • 81
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    Journal of Physical Organic Chemistry 11 (1998), S. 201-208 
    ISSN: 0894-3230
    Keywords: indolizines ; cycloaddition ; reaction mechanism ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The peculiarities of [8+2] cycloaddition reactions of indolizines with dienophiles are reviewed. Quantum chemical SINDO1, AM1 and ab initio calculations of transition states were performed for [8+2] cycloaddition reactions of indolizine and 6-nitroindolizine with a series of alkenes with donor and acceptor groups. The calculations predict a dipolar cycloaddition mechanism (electrophilic addition and ring closure) for reactions of indolizine and 6-nitroindolizine with nitroethylene. For the reaction of 6-nitroindolizine with N,N-dimethylaminoethylene, the predicted mechanism corresponds to a previously unknown ‘inverse’ dipolar cycloaddition (nucleophilic addition and ring closure). © 1998 John Wiley & Sons, Ltd.
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  • 82
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    Journal of Physical Organic Chemistry 11 (1998), S. 115-124 
    ISSN: 0894-3230
    Keywords: cross-interaction constants ; gas-phase nucleophilic substitution reactions ; PM3 MO ; benzyl chlorides ; phenoxides ; thiophenoxides ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gas-phase nucleophilic substitution reactions of Y-benzyl chlorides with X-phenoxide and X-thiophenoxide nucleophiles were investigated theoretically using the PM3 semi-empirical MO method. The Leffler-Grunwald rate-equilibrium and Brønsted correlations predict that the degree of bond formation in the transition state (TS) is approximately 45 and 40% on the reaction coordinate for the phenoxides and thiophenoxides, respectively. For a weaker nucleophile, a later TS is obtained with an increased bond making and breaking. The variation of the TS structure with substituents in the nucleophile is thermodynamically controlled and is well correlated by rate-equilibrium relationships. In contrast, the TS variation (a tighter TS) with substituent (for a stronger acceptor Y) in the substrate is dependent only on variations of the intrinsic barrier and so cannot be correlated by such thermodynamically based rate-equilibrium relationships. The gas phase ρX and ρY values are much greater in magnitude than those in solution. A similar gas-phase theoretical cross-interaction constant, ρXY (ca -0.60), is obtained for both phenoxides and thiophenoxides, which is in good agreement with the experimental value (-0.62) for the thiophenoxide reactions in MeOH at 20.0 °C. The oxy and sulfur anion bases lead to a similar TS structure, but a lower reactivity for the former is due to a greater endothermicity of the reaction. A relatively wide range variation of the reaction energies, ΔG°, can be ascribed to the loss of resonance stabilization of anion nucleophiles upon product formation. © 1998 John Wiley & Sons, Ltd.
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  • 83
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    Journal of Physical Organic Chemistry 11 (1998), S. 171-176 
    ISSN: 0894-3230
    Keywords: acetaldehyde ; oxidation ; periodate ; osmium (VIII) catalysis ; ruthenium (III) catalysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Os(VIII) and Ru(III) catalysis of the periodate oxidation of acetaldehyde in aqueous alkaline medium was investigated. The catalytic efficiency is Ru(III)〈Os(VIII). The product of oxidation in both cases is acetate and IO3-. The stoichiometry is the same in both catalyzed reactions, i.e. [IO4-]:[CH3CHO] = 1:1. Probable mechanisms are proposed and discussed. The reaction constants involved in the mechanisms are derived. © 1998 John Wiley & Sons, Ltd.
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  • 84
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    Journal of Physical Organic Chemistry 11 (1998), S. 223-229 
    ISSN: 0894-3230
    Keywords: Solvolysis ; Grunwald-Winstein-type analysis ; Hammett-type analysis ; YxBnCl scale ; 1-aryl-1-phenylmethyl cations ; Mulliken population analysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rate constants of solvolysis of α-tert-butyl(2-naphthyl)methyl chloride (1), 9-fluorenyl chloride (2) and a series of monosubstituted benzhydryl chlorides (3) in a wide range of solvents were measured. Grunwald-Winstein-type correlation analysis of log k for 2 and 3 against YBnCl, with or without nucleophilicity N, yielded less satisfactory linear correlations than that against log k(1). A new scale of solvent ionizing power, YxBnCl, for the correlation of solvolytic reactivities of benzylic chlorides with extended charge delocalization based on log k(1) was developed. Application to the mechanistic study suggested the solvolysis of 2 and 4-nitrobenzhydryl chloride were non-limiting. Hammett plots against σ+ constants exhibited more negative ρ values in less nucleophilic solvents. In a benzhydryl chloride containing a strong deactivating substituent, such as 4-nitro, the positive charge delocalizes mainly over the unsubstituted ring in the cationic transition state. The uneven charge distribution was also confirmed by Mulliken population analysis at the level of the RHF/6-31G*//RHF/3-21G(*) basis set for cations. Comparison of the results of correlation analysis using the equation log(k/k0) = mY vs the equation log(k/k0) = mY+hI, and using the equation log(k/k0) = mY+lN vs the equation log(k/k0) = mY+lN+hI indicated the use of YBnCl or YxBnCl could give a better understanding of solvolytic mechanisms than the combinatorial use of YCl and I. © 1998 John Wiley & Sons, Ltd.
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  • 85
    ISSN: 0894-3230
    Keywords: Solvent-solute interactions ; β-carotene ; electronic absorption spectrum ; solvent effects ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solvent effects on the wavenumber of the maximum of the longest wavelength electronic absorption band of all-trans-β-carotene were determined in 34 solvents. Together with results from previous studies, a data set for 51 solvents, mostly non-hydrogen bond donors, was constructed. This information was analyzed in terms of reaction field models and also showed its value for correlation purposes when used either alone or in combination with standard empirical solvent polarity-polarizability scales. © 1998 John Wiley & Sons, Ltd.
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  • 86
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    Journal of Physical Organic Chemistry 11 (1998), S. 177-184 
    ISSN: 0894-3230
    Keywords: nitro derivatives of phenols ; pyrolysis initiation reactions ; impact sensitivity ; UHF-SCF-AM1 MO method ; activation energy. ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The UHF-SCF-AM1 MO method was applied to the study of two kinds of pyrolysis reactions of six nitro derivatives of phenols (homolysis reaction by rupture of the C - NO2 bond into radicals and isomerization reaction involving phenolic hydrogen transferring to oxygen on the NO2 group). The molecular geometries of reactants, transition states and products were fully optimized. The potential energy curves and activation energies were first obtained. The results show that this category of compounds is more easily initiated via isomerization reactions than by homolysis reactions. The parallel relationship among the Wiberg bond order of the pyrolysis-initiation H - O bond in the molecule of a reactant, the activation energy of the isomerization reaction breaking the H - O bond and impact sensitivity of the reactant gives ‘the principle of the smallest bond order’ (PSBO) powerful support. The sensitizing effect of a phenol group was elucidated based on calculation results. The different influences of OH and NO2 groups on the heat of formation of a molecule are discussed. © 1998 John Wiley & Sons, Ltd.
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  • 87
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    Journal of Physical Organic Chemistry 11 (1998), S. 216-222 
    ISSN: 0894-3230
    Keywords: o-carboxybenzohydroxamic acid ; phthalic anhydride ; phthalic acid ; hydrolysis ; intramolecular acid catalysis ; kinetics ; activation parameters ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Phthalic anhydride was detected spectrophotometrically in the hydrolysis of o-carboxybenzohydroxamic acid (OCBA) in CH3CN-H2O solvent containing 0.03 mol dm-3 HCl. Pseudo-first-order rate constants (k1) for hydrolysis of OCBA are almost independent of the change in CH3CN content from 10 to 80% (v/v) in mixed aqueous solvents. The rate constants k1 are more than 10-fold larger than the corresponding rate constants for hydrolysis of phthalamic acid. These observations are explained in terms of a mechanism slightly different from the mechanism for hydrolysis of phthalamic acid. The activation parameters, ΔH* and ΔS*, are not affected appreciably by an increase in CH3CN content from 10 to 80% in mixed aqueous solvents. © 1998 John Wiley & Sons, Ltd.
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  • 88
    ISSN: 0894-3230
    Keywords: solute-solvent interactions ; solvent-solvent interactions ; binary solvents ; alcohol-water mixtures ; water structure ; solvatochromic indicators ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A preferential solvation model that takes into account the enhancement of the structure of water when small amounts of alcohol are added was applied to solvatochromic data for binary mixtures of water with 2-methylpropan-2-ol, propan-2-ol, ethanol and methanol. Application of the model allows the calculation of the effect of the enhancement of the water structure on solvatochromic solvent properties. It is demonstrated that the enhancement of water structure increases the solvent dipolarity/polarizability and hydrogen-bond donor acidity and decreases the solvent hydrogen-bond acceptor basicity. The effect decreases in the order 2-methylpropan-2-ol-water, propan-2-ol-water, ethanol-water and methanol-water. © 1998 John Wiley & Sons, Ltd.
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  • 89
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    Journal of Physical Organic Chemistry 11 (1998), S. 157-170 
    ISSN: 0894-3230
    Keywords: heterolytic bond dissociation energy ; carbon-carbon σ bonds ; hydrocarbons ; structural dependence ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The coordination of a resonance-stabilized hydrocarbon cation and anion yielded a series of unprecedented hydrocarbons, which are susceptible to thermal heterolytic cleavage of carbon-carbon σ bonds in polar media, generating the original ions under reversible conditions. When the component ions were sufficiently stabilized, some ion pairs were even isolated as solids, thus providing the first examples of hydrocarbon salts. The direct observation of the heterolysis by means of spectroscopy permitted reliable thermodynamic treatments of the observed degree of ionic dissociation. Correlation of the free energy of heterolysis with solvent dielectric constants and parameters of ion stabilities such as pKHA, pKR+ and redox potentials revealed the importance of the thermodynamic stabilities of ions, the degree of solvation and steric congestion in the starting molecule as major controlling factors in the heterolysis. © 1998 John Wiley & Sons, Ltd.
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  • 90
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    Journal of Physical Organic Chemistry 11 (1998), S. 273-276 
    ISSN: 0894-3230
    Keywords: N,N-diphenylcarbamoylpyridinium ion ; solvolysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solvolyses of the N,N-diphenylcarbamoylpyridinium ion are subject to specific and/or general base catalysis, which can be eliminated by addition of perchloric acid or increased, especially in fluoroalcohol-containing solvents, by addition of pyridine. The uncatalyzed solvolyses in aqueous methanol and aqueous ethanol involve a weakly nucleophilically assisted (l  =  0.22) heterolysis and the solvolyses in the pure alcohols are anomalously slow. © 1998 John Wiley & Sons, Ltd.
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  • 91
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    Journal of Physical Organic Chemistry 11 (1998), S. 209-215 
    ISSN: 0894-3230
    Keywords: securinine ; cationic micelles ; anionic micelle ; non-ionic micelle ; alkaline hydrolysis ; kinetics ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of micelles of cetyltrimethylammonium bromide (CTABr), tetradecyltrimethylammonium bromide (TTABr), sodium dodecyl sulfate (SDS) and polyoxyethylene 10 lauryl ether (C12E10) on the rates of alkaline hydrolysis of securinine were studied at a constant [-OH] (0.05 M). An increase in the total concentrations of CTABr, TTABr, SDS and C12E10 from 0.0 to 0.2 M causes a decrease in the observed pseudo-first-order rate constants (kobs) by factors of ca 2.5, 3, 7 and 4, respectively. The observed data are explained in terms of pseudophase and pseudophase ion-exchange (PIE) models of micelle. The binding constants, KS, of securinine with SDS, C12E10, CTABr and TTABr micelles are 32.4, 14.8, 22.1, and 9.1 M-1, respectively. The magnitudes of the second-order rate constants, kM, for the reactions in the micellar pseudophase are negligible compared with the corresponding rate constant, kW, for the reaction occurring in the aqueous pseudophase for CTABr, TTABr, SDS and C12E10. © 1998 John Wiley & Sons, Ltd.
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  • 92
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    Journal of Physical Organic Chemistry 11 (1998), S. 277-282 
    ISSN: 0894-3230
    Keywords: colloidal CdS-induced photochemical reactions ; photocatalytic reactions ; photooxidation ; 2-methylindole ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 2-Methylindole (2-MI) is adsorbed on the surface of colloidal CdS particles with an adsorption intensity of 0.6 × 103 dm3 mol-1. A new emission band at 530 nm is produced by forming an exciplex between excited CdS and 2-MI and the red emission due to CdS is simultaneously quenched. The emission maxima of green bands for different indoles increase in the order indole 〈 tryptophan 〈 2-MI 〈 3-MI and are observed at 508, 520, 530 and 540 nm, respectively. The shift in emission maxima is related to the oxidation potential of these substrates. The irradiation of an aerated reaction mixture containing CdS and 2-MI with visible light induces the oxidation of adsorbed 2-MI by photogenerated holes to produce 2-methyl-3-indolinone and 2-acetamidobenzaldehyde. The latter product is formed due to oxidative C - C bond cleavage of the pyrrole ring. The reactivity of trapped holes towards the adsorbed 2-MI is evidenced by a decrease in the lifetime of the red emission of CdS in the presence of 2-MI. In this reaction the possibility of the participation of singlet oxygen is ruled out. A general mechanism of CdS-induced oxidation of indoles is discussed. © 1998 John Wiley & Sons, Ltd.
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  • 93
    ISSN: 0894-3230
    Keywords: crown dithioether ; conformational analysis ; multicomponent equilibrium ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The solid-state molecular structure and the conformational behaviour in solution of the 12-membered crown dithioether 8-methyl-1,4-dioxa-7,10-dithiacyclododecane-5,12-dione were studied by x-ray crystallography, 1H and 13C NMR spectroscopy and molecular mechanics. The conformational rigidity of some constituent structural fragments allowed a detailed analysis of the structure and distribution of the conformers. A protocol for studies of multiconformational equilibrium was developed by means of the combined use of structure calculations and dynamic NMR measurements. © 1998 John Wiley & Sons, Ltd.
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  • 94
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    Journal of Physical Organic Chemistry 11 (1998), S. 321-333 
    ISSN: 0894-3230
    Keywords: metal-catalyzed carbenoid reactions ; iodonium ylides ; sulfonium ylides ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Transition metal-catalyzed decomposition of phenyliodonium and diphenylsulfonium ylides was investigated with regard to application in asymmetric carbenoid reactions. Phenyliodonium ylides react in the presence of Rh(II) catalysts with the same selectivity in inter- and intramolecular cyclopropanations as the corresponding diazo compounds, and intramolecular CH insertions proceed with identical enantioselectivities. With diphenylsulfonium ethoxycarbonylmethylide the Cu(I)-catalyzed cyclopropanation of olefins affords trans/cis ratios and asymmetric inductions identical with those of diazo compounds, but with Rh(II) catalysts some small, although significant, selectivity variations occur, which are ascribed to coordination of diphenyl sulfide to one of the coordination sites of the catalyst. © 1998 John Wiley & Sons, Ltd.
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  • 95
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    Journal of Physical Organic Chemistry 11 (1998), S. 299-304 
    ISSN: 0894-3230
    Keywords: molecular architecture ; molecule-based magnets ; biopolymers ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Application of the principles of physical organic chemistry to the construction of molecule-based magnets is discussed. Not only the magnetic structures of conventional magnets but also secondary and tertiary structures of biopolymers are instrumental in the molecular design. © 1998 John Wiley & Sons, Ltd.
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  • 96
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    Journal of Physical Organic Chemistry 11 (1998), S. 350-355 
    ISSN: 0894-3230
    Keywords: 1,3-dipoles ; cumulenes ; infrared spectroscopy ; mass spectrometry ; flash vacuum thermolysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the direct investigation of reactive intermediates it is particularly valuable to use a combination of several spectroscopic techniques. This commentary highlights recent examples, using primarily flash vacuum thermolysis for the generation of the intermediates, and matrix IR spectroscopy in conjunction with gas-phase mass spectrometric methods for their identification. The examples include nitrile imines, nitrile ylides, nitrile sulfides and selenides, dinitrogen sulfide and several novel cumulenes (X=C=C=Y, RN=C=C=C=X). © 1998 John Wiley & Sons, Ltd.
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  • 97
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    Journal of Physical Organic Chemistry 11 (1998), S. 305-320 
    ISSN: 0894-3230
    Keywords: poly(alkylmethyldiallylammonium halides) ; aggregation behavior ; polyelectrolytes ; polysoaps ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hydrophobically modified polyelectrolytes (polysoaps) are a unique class of water-soluble polymers containing distinct hydrophobic and hydrophilic regions. Above a certain concentration, polysoaps form intramolecular and intermolecular aggregates in aqueous solution. They have attracted much attention not only for their ability to mimic some functions demonstrated by biopolymers but also for their important industrial applications. This review highlights some interesting features of novel non-cross-linked and cross-linked poly(alkylmethyldiallylammonium halides) that have been described in recent years. © 1998 John Wiley & Sons, Ltd.
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  • 98
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    Journal of Physical Organic Chemistry 11 (1998), S. 334-340 
    ISSN: 0894-3230
    Keywords: brain chemistry ; membrane proteins ; molecular neurobiology ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Efforts to developed detailed insights into the structure and function of the molecules of memory, thought and sensory perception - physical organic chemistry on the brain - are described. By combining more conventional chemical tools with a number of techniques adapted from modern biology, it is now possible to perform systematic structure-function studies on the integral membrane proteins that play a central role in molecular neurobiology. There are substantial challenges associated with such studies, but we believe the potential payoff is considerable. © 1998 John Wiley & Sons, Ltd.
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  • 99
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    Journal of Physical Organic Chemistry 11 (1998), S. 341-349 
    ISSN: 0894-3230
    Keywords: vicarious nucleophilic substitution ; hydrogen ; mechanism ; orientation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hydrogens located at activated positions in electrophilic arenes, e.g. ortho and para hydrogens in nitrobenzenes, can be replaced with a nucleophile moiety provided there is at least one nucleofuge X connected to the nucleophilic centre. As the group really leaving in this hydrogen substitution process is not the hydride anion but X, the reaction has been named vicarious nucleophilic substitution of hydrogen (VNS). The concepts on the mechanism of the reaction and their experimental background are presented. Reactivity and orientation - the fundamental questions concerning synthetical applications of VNS - are discussed in light of the supposed mechanistic picture.
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  • 100
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    Journal of Physical Organic Chemistry 11 (1998), S. 291-291 
    ISSN: 0894-3230
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No Abstract
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