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  • American Institute of Physics (AIP)
  • Cambridge University Press
  • 2005-2009  (7,384)
  • 1985-1989  (42,610)
  • 1980-1984  (9,518)
  • 1960-1964  (3,736)
  • 1950-1954  (1,787)
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Years
Year
  • 1
    Unknown
    Cambridge, U.K ; New York, N.Y : Cambridge University Press
    Keywords: Cellular telephone services industry ; Electronic books ; Mobile communication systems, Economic aspects ; Wireless communication systems, Economic aspects
    Pages: 1 v. (various pagings)
    ISBN: 0-511-11564-4
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  • 2
    Unknown
    Cambridge ; New York : Cambridge University Press
    Keywords: Shakespeare, William, Tragedies ; Electronic books ; Identity (Psychology) in literature ; Tragedy ; Violence in literature
    Pages: ix, 228 p.
    ISBN: 0-511-11352-8
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  • 3
    Unknown
    New York : Cambridge University Press
    Keywords: Capital market ; Electronic books ; Futures market ; Stock exchanges
    Pages: 1 v. (various pagings)
    ISBN: 0-511-11580-6
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  • 4
    Keywords: Developing countries, Economic policy. ; Federal government, Developing countries.
    Pages: xi, 276 p.
    ISBN: 0-511-11566-0
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  • 5
    Unknown
    Cambridge ; New York : Cambridge University Press
    Keywords: Dynamics. ; Kinematics.
    Pages: x, 374 p.
    Edition: 3rd ed
    ISBN: 0-511-11583-0
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  • 6
    Unknown
    Cambridge ; New York : Cambridge University Press
    Keywords: Shakespeare, William, Language ; Shakespeare, William, Romeo and Juliet ; Shakespeare, William, Stage history, 1950- ; Shakespeare, William, Stage history, England, London ; Electronic books ; English language, Pronunciation, Early modern, 1500-1700 ; Globe Theatre (London, England : 1996- )
    Pages: xviii, 188 p.
    ISBN: 0-511-11364-1
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  • 7
    Unknown
    Cambridge, U.K ; New York : Cambridge University Press
    Keywords: Electronic books ; Religion, Study and teaching (Higher) ; Theology, Study and teaching (Higher)
    Pages: xvii, 230 p.
    ISBN: 0-511-11355-2
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  • 8
    Unknown
    Cambridge [England] ; New York : Cambridge University Press
    Keywords: Engineering mathematics, Data processing. ; Numerical analysis, Data processing. ; MATLAB.
    Pages: viii, 426 p.
    ISBN: 0-511-12811-8
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  • 9
    Unknown
    New York : Cambridge University Press
    Keywords: Materials, Mechanical properties.
    Pages: xx, 425 p.
    ISBN: 0-511-11575-X
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  • 10
    Unknown
    Cambridge, UK ; New York : Cambridge University Press
    Keywords: Autonomy (Psychology) ; Electronic books ; Ethics, Modern
    Notes: Planning agency, autonomous agency / Michael E. Bratman -- Autonomy without free will / Bernard Berofsky -- Autonomy and the paradox of self-creation : infinite regresses, finite selves, and the limits of authenticity / Robert Noggle -- Agnostic autonomism revisited / Alfred R. Mele -- Feminist intuitions and the normative substance of autonomy / Paul Benson -- Autonomy and personal integration / Laura Waddell Ekstrom -- Responsibility, applied ethics, and complex autonomy theories / Nomy Arpaly -- Autonomy and free agency / Marina A.L. Oshana -- The relationship between autonomous and morally responsible agency / Michael McKenna -- Alternative possibilities, personal autonomy, and moral responsibility / Ishtiyaque Haji -- Freedom within reason / Susan Wolf -- Procedural autonomy and liberal legitimacy / John Christman -- The concept of autonomy in bioethics : an unwarranted fall from grace / Thomas May -- Who deserves autonomy, and whose autonomy deserves respect? / Tom L. Beauchamp -- Autonomy, diminished life, and the threshold for use / R.G. Frey
    Pages: ix, 350 p.
    ISBN: 0-511-08224-X
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  • 11
    Unknown
    Cambridge, UK ; New York : Cambridge University Press
    Keywords: Kant, Immanuel,, 1724-1804. ; Causation.
    Pages: xi, 451 p.
    ISBN: 0-511-08217-7
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  • 12
    Unknown
    Cambridge, UK ; New York : Cambridge University Press
    Keywords: Monte Carlo method. ; Statistical physics.
    Pages: xv, 432 p.
    Edition: 2nd ed
    ISBN: 0-511-13098-8
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  • 13
    Unknown
    Cambridge ; New York : Cambridge University Press
    Keywords: Equality. ; Minorities. ; Minorities, Civil rights. ; Multiculturalism. ; Social conflict. ; Social groups.
    Pages: xii, 390 p.
    ISBN: 0-511-08065-4
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  • 14
    Unknown
    Cambridge, UK ; New York : Cambridge University Press
    Keywords: Frege, Gottlob,, 1848-1925.
    Notes: Biography -- Function and argument -- Sense and reference -- Frege's Begriffsschrift theory of identity -- Concept and object -- Names and descriptions -- Existence -- Thought, truth value and assertion -- Indirect reference -- Through the quotation marks
    Pages: xix, 226 p.
    ISBN: 0-511-10977-6
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  • 15
    Unknown
    Cambridge : Cambridge University Press
    Keywords: Space time codes.
    Pages: 1 v. (various pagings)
    ISBN: 0-511-11562-8
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  • 16
    Publication Date: 2017-04-04
    Description: Twenty eruptive events from the Northeast Crater of Stromboli volcano recorded by a thermal monitoring camera in early 2004 were analysed in order to understand the eruptive dynamics. Selected eventswere chosen to be typical of explosions that characterize the steady activity of Stromboli in terms of jet height and duration. Most of the explosions consisted of clast-rich single bursts, originating from the same vent inside the Northeast Crater. Conspicuous ash emission was scarce. Eruptions were preceded by the flashing of a perturbation wave characterized by low temperatures and an average propagation velocity of about 35–100 m s−1. This perturbation was thought to be caused by the bursting of the gas slug at the bottom of the crater and is interpreted as an air wave. This was immediately followed by the expansion of a jet of ‘hot’ gas and particles, at a velocity of 35–75 m s−1. Ejecta coarser than 138 cm appeared ∼1.6–2 s after the onset of the explosion, moving at a variable velocity (30–60 m s−1). Eruptive events were either vertical or inclined 7–13◦ towards the NNW. This inclination is thought to be a consequence either of the morphology of the conduit, following modest rock falls that partially obstructed the uppermost part of the crater, or of the displacement of the internal conduit due to the explosive activity of the volcano. The instability of the summit area is a further possible cause of the deformation of the conduit.
    Description: This work was partially funded by the Istituto Nazionale di Geofisica e Vulcanologia and the Dipartimento della Protezione Civile, Italy, project INGVDPC V2
    Description: Published
    Description: 591–601
    Description: 1.5. TTC - Sorveglianza dell'attività eruttiva dei vulcani
    Description: 1.10. TTC - Telerilevamento
    Description: 3.6. Fisica del vulcanismo
    Description: JCR Journal
    Description: reserved
    Keywords: explosive dynamic ; thermal video monitoring ; volcano-tectonic structures ; volcano collapses ; Stromboli ; 04. Solid Earth::04.04. Geology::04.04.99. General or miscellaneous ; 04. Solid Earth::04.04. Geology::04.04.11. Instruments and techniques ; 04. Solid Earth::04.07. Tectonophysics::04.07.99. General or miscellaneous ; 04. Solid Earth::04.07. Tectonophysics::04.07.05. Stress ; 04. Solid Earth::04.07. Tectonophysics::04.07.07. Tectonics ; 04. Solid Earth::04.07. Tectonophysics::04.07.08. Volcanic arcs ; 04. Solid Earth::04.08. Volcanology::04.08.99. General or miscellaneous ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 04. Solid Earth::04.08. Volcanology::04.08.02. Experimental volcanism ; 04. Solid Earth::04.08. Volcanology::04.08.03. Magmas ; 04. Solid Earth::04.08. Volcanology::04.08.04. Thermodynamics ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 04. Solid Earth::04.08. Volcanology::04.08.07. Instruments and techniques ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk ; 05. General::05.02. Data dissemination::05.02.99. General or miscellaneous ; 05. General::05.02. Data dissemination::05.02.03. Volcanic eruptions ; 05. General::05.08. Risk::05.08.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 17
    Publication Date: 2022-05-25
    Description: Author Posting. © Cambridge University Press, 2000. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Journal of Fluid Mechanics 403 (2000): 37-65, doi:10.1017/S0022112099006916.
    Description: The dynamics of expanding domes of isothermal lava are studied by treating the lava as a viscoplastic material with the Herschel–Bulkley constitutive law. Thin-layer theory is developed for radially symmetric extrusions onto horizontal plates. This provides an evolution equation for the thickness of the fluid that can be used to model expanding isothermal lava domes. Numerical and analytical solutions are derived that explore the effects of yield stress, shear thinning and basal sliding on the dome evolution. The results are briefly compared with an experimental study. It is found that it is difficult to unravel the combined effects of shear thinning and yield stress; this may prove important to studies that attempt to infer yield stress from morphology of flowing lava.
    Description: The financial support of an EPSRC Advanced Fellowship is gratefully acknowledged by R.V. C. N. J. B. was partially supported by the NSF Grant OCE-9616017 and an EPSRC Visiting Fellowship Grant GR/M50409.
    Keywords: Isothermal lava domes
    Repository Name: Woods Hole Open Access Server
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  • 18
    Publication Date: 2022-05-25
    Description: Author Posting. © Cambridge University Press, 2004. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Parasitology 128 (2004): 577-584, doi:10.1017/S0031182004005025.
    Description: Human serum high-density lipoprotein (HDL) is necessary and sufficient for the short-term maintenance of Plasmodium falciparum in in vitro culture. However, at high concentrations it is toxic to the parasite. A heat-labile component is apparently responsible for the stage-specific toxicity to parasites within infected erythrocytes 12–42 h after invasion, i.e. during trophozoite maturation. The effects of HDL on parasite metabolism (as determined by nucleic acid synthesis) are evident at about 30 h after invasion. Parasites treated with HDL show gross abnormalities by light and electron microscopy.
    Description: Professor Hajduk was supported by NIH. Professor Day was supported by a Research Leave Fellowship from The Wellcome Trust. Dr Imrie and Ms Carter were supported by Programme Grant funding awarded to Professor Day from The Wellcome Trust. Dr Ferguson was supported by an equipment grant from The Wellcome Trust.
    Keywords: Plasmodium falciparum ; High density lipoprotein
    Repository Name: Woods Hole Open Access Server
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  • 19
    Publication Date: 2022-05-25
    Description: Author Posting. © Cambridge University Press, 2004. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Geological Magazine 141 (2004): 195-207, doi:10.1017/S001675680400891X.
    Description: Because magmatism associated with subduction is thought to be the principal source for continental crust generation, assessing the relative contribution of pre-existing (subducted and assimilated) continental material to arc magmatism in accreted arcs is important to understanding the origin of continental crust. We present a detailed Nd isotopic stratigraphy for volcanic and volcaniclastic formations from the South Mayo Trough, an accreted oceanic arc exposed in the western Irish Caledonides. These units span an arc–continent collision event, the Grampian (Taconic) Orogeny, in which an intra-oceanic island arc was accreted onto the passive continental margin of Laurentia starting at [similar] 475 Ma (Arenig). The stratigraphy corresponding to pre-, syn- and post-collisional volcanism reveals a progression of [varepsilon]Nd(t) from strongly positive values, consistent with melt derivation almost exclusively from oceanic mantle beneath the arc, to strongly negative values, indicating incorporation of continental material into the melt. Using [varepsilon]Nd(t) values of meta-sediments that represent the Laurentian passive margin and accretionary prism, we are able to quantify the relative proportions of continent-derived melt at various stages of arc formation and accretion. Mass balance calculations show that mantle-derived magmatism contributes substantially to melt production during all stages of arc–continent collision, never accounting for less than 21% of the total. This implies that a significant addition of new, rather than recycled, continental crust can accompany arc–continent collision and continental arc magmatism.
    Keywords: Grampian Orogeny ; Western Ireland ; Continental crust ; Nd isotopes ; Laurentia ; Iapetus Ocean
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  • 20
    Publication Date: 2022-05-25
    Description: Author Posting. © Cambridge University Press, 2007. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Journal of Fluid Mechanics 574 (2007): 465-493, doi:10.1017/S0022112006004216.
    Description: Acoustic Doppler velocity profiler (ADVP) measurements of instantaneous three-dimensional velocity profiles over the entire turbulent boundary layer height, δ, of rough-bed open-channel flows at moderate Reynolds numbers show the presence of large scale coherent shear stress structures (called LC3S herein) in the zones of uniformly retarded streamwise momentum. LC3S events over streamwise distances of several boundary layer thicknesses dominate the mean shear dynamics. Polymodal histograms of short streamwise velocity samples confirm the subdivision of uniform streamwise momentum into three zones also observed by Adrian et al. (J. Fluid Mech., vol. 422, 2000, p. 1). The mean streamwise dimension of the zones varies between 1δ and 2.5δ. In the intermediate region (0.2〈z/δ〈0.75), the contribution of conditionally sampled u'w' events to the mean vertical turbulent kinetic energy (TKE) flux as a function of threshold level H is found to be generated by LC3S events above a critical threshold level Hmax for which the ascendant net momentum flux between LC3S of ejection and sweep types is maximal. The vertical profile of Hmax is nearly constant over the intermediate region, with a value of 5 independent of the flow conditions. Very good agreement is found for all flow conditions including the free-stream shear flows studied in Adrian et al. (2000). If normalized by the squared bed friction velocity, the ascendant net momentum flux containing 90% of the mean TKE flux is equal to 20% of the shear stress due to bed friction. In the intermediate region this value is nearly constant for all flow conditions investigated herein. It can be deduced that free-surface turbulence in open-channel flows originates from processes driven by LC3S, associated with the zonal organization of streamwise momentum. The good agreement with mean quadrant distribution results in the literature implies that LC3S identified in this study are common features in the outer region of shear flows.
    Description: The study was supported by the Swiss National Foundation for Scientific Research for the experimental part (grant 2100 050739) and the French National Center for Scientific Research (CNRS) for the data analysis and interpretation.
    Repository Name: Woods Hole Open Access Server
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  • 21
    Publication Date: 2022-05-25
    Description: Author Posting. © Cambridge University Press, 2005. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Journal of Fluid Mechanics 540 (2005): 49-73, doi:10.1017/S002211200500577X.
    Description: Circulation driven by horizontal differential heating is studied, using a double-walled Plexiglas tank (20×15×2.5 cm3) filled with salt water. For instances of heating/cooling from above and below, results indicate that there is always quasi-equilibrium circulation. In contrast to most previous results from experimental/ numerical studies, circulation in our experiments appears in the form of a shallow cell adjacent to the boundary of thermal forcing. The non-dimensional stream-function maximum confirms the 1/5-power law of Rossby, Ψ ∼Ra1/5 L . Dissipation rate measured in the experiments appears to be consistent with theory. For cases of heating/cooling from a sloping bottom, circulation is similar to cases with a flat bottom; circulation is strong if heating is below cooling, but it is rather weak if heating is above cooling. Nevertheless, circulation in all cases is visible to the naked eye.
    Description: W. W. was supported by The National Natural Science Foundation of China through grant 40476010 and the Research Fund for the Doctoral Program of Higher Education through grant 20030423011. R. X. H. was supported by the National Science Foundation through grant OCE-0094807 and the National Aero- Space Administration through Contract 1229833 (NRA-00-OES-05) to the Woods Hole Oceanographic Institution.
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  • 22
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    Cambridge University Press
    Publication Date: 2022-05-25
    Description: Author Posting. © Cambridge University Press, 2008. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Journal of Fluid Mechanics 602 (2008): 241-266, doi:10.1017/S0022112008000827.
    Description: The stability of a hydraulically driven sill flow in a rotating channel with smoothly varying cross-section is considered. The smooth topography forces the thickness of the moving layer to vanish at its two edges. The basic flow is assumed to have zero potential vorticity, as is the case in elementary models of the hydraulic behaviour of deep ocean straits. Such flows are found to always satisfy Ripa's necessary condition for instability. Direct calculation of the linear growth rates and numerical simulation of finite-amplitude behaviour suggests that the flows are, in fact, always unstable. The growth rates and nonlinear evolution depend largely on the dimensionless channel curvature κ=2αg′/f2, where 2α is the dimensional curvature, g′ is the reduced gravity, and f is the Coriolis parameter. Very small positive (or negative) values of κ correspond to dynamically wide channels and are associated with strong instability and the breakup of the basic flow into a train of eddies. For moderate or large values of κ, the instability widens the flow and increases its potential vorticity but does not destroy its character as a coherent stream. Ripa's condition for stability suggests a theory for the final width and potential vorticity that works moderately well. The observed and predicted growth in these quantities are minimal for κ≥1, suggesting that the zero-potential-vorticity approximation holds when the channel is narrower than a Rossby radius based on the initial maximum depth. The instability results from a resonant interaction between two waves trapped on opposite edges of the stream. Interactions can occur between two Kelvin-like frontal waves, between two inertia–gravity waves, or between one wave of each type. The growing disturbance has zero energy and extracts zero energy from the mean. At the same time, there is an overall conversion of kinetic energy to potential energy for κ〉0, with the reverse occurring for κ〈0. When it acts on a hydraulically controlled basic state, the instability tends to eliminate the band of counterflow that is predicted by hydraulic theory and that confounds hydraulic-based estimates of volume fluxes in the field. Eddy generation downstream of the controlling sill occurs if the downstream value of κ is sufficiently small.
    Description: This work was supported by the National Science Foundation (Grant OCE- 0525729).
    Repository Name: Woods Hole Open Access Server
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  • 23
    Publication Date: 2022-05-25
    Description: Author Posting. © Cambridge University Press, 2004. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Journal of Fluid Mechanics 516 (2004): 83-113, doi:10.1017/S0022112004000473.
    Description: Oceanic observations indicate that abyssal mixing tends to be localized to regions of rough topography. How localized mixing interacts with the ambient fluid in a stratified, rotating system is an open question. To gain insight into this complicated process laboratory experiments are used to explore the interaction of mechanically induced boundary mixing and an interior body of linearly stratified rotating fluid. Turbulence is generated by a single vertically oscillating horizontal bar of finite horizontal extent, located at mid-depth along the tank wall. The turbulence forms a region of mixed fluid which quickly reaches a steady-state height and collapses into the interior. The mixed-layer thickness, $h_m\,{\sim}\,\gamma ({\omega}/{N})^{1/2}$, is spatially uniform and independent of the Coriolis frequency $f$. $N$ is the initial buoyancy frequency, $\omega$ is the bar oscillation frequency, and $\gamma\,{\approx}\,1$ cm is an empirical constant determined by the bar geometry. Surprisingly, the export of mixed fluid does not occur as a boundary current along the tank perimeter. Rather, mixed fluid intrudes directly into the interior as a radial front of uniform height, advancing with a speed comparable to a gravity current. The volume of mixed fluid grows linearly with time, $V\,{\propto}\,({N}/{f})^{3/2}h_m^3 \textit{ft}$, and is independent of the lateral extent of the mixing bar. Entrainment into the turbulent zone occurs principally through horizontal flows at the level of the mixing that appear to eliminate export by a geostrophic boundary flow. The circulation patterns suggest a model of unmixed fluid laterally entrained at velocity $u_e \,{\sim}\,Nh_m $ into the open sides of a turbulent zone with height $h_{m}$ and a length, perpendicular to the boundary, proportional to $L_f \,{\equiv}\,\gamma ({\omega}/{f})^{1/2}$. Here $L_{f}$ is an equilibrium length scale associated with rotational control of bar-generated turbulence. The model flux of exported mixed fluid $Q\,{\sim}\,h_m L_f u_e$ is constant and in agreement with the experiments.
    Description: This work was supported by the Ocean Ventures Fund, the Westcott Fund and the WHOI Academic Programs Office. Financial support was also provided by the National Science Foundation through grant OCE-9616949.
    Keywords: Abyssal mixing ; Stratified rotating system
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  • 24
    Publication Date: 2022-05-25
    Description: Author Posting. © Cambridge University Press, 2004. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Journal of Fluid Mechanics 506 (2004): 217-244, doi:10.1017/S0022112004008572.
    Description: The effect of both vertical and horizontal components of the Earth's rotation on plumes during deep convection in the ocean is studied. In the laboratory, the misalignment, characterized by the angle $\alpha$, between the buoyancy force (‘effective’ free-fall acceleration ${\bm g}_e$) and the rotation axis ${\bm \Omega}$ is produced by using the centrifugal force: an experimental tank was placed at a large distance from the centre of the turntable. The mathematical analogy between the laboratory model and the oceanic environment is presented. For $\alpha\,{=}\,30^\circ$, a number of laboratory experiments spanning a wide range of the buoyancy flux parameter, and correspondingly Reynolds number, is used to illustrate the development of the convective plume from a point source in regimes ranging from weakly to highly turbulent. New features of the flow, as compared to $\alpha\,{=}\,0$, are documented and explained. The incoming heavier dyed fluid jet disintegrates into fast-sinking coherent blobs (in a low-Reynolds-number regime) or turbulent billows (in a high-Reynolds-number regime) and a more diffuse cloud of highly diluted dyed water. An analysis of the forces acting on an ellipsoid moving in a rotating fluid with the main balance including the buoyancy, Coriolis forces, and the hydrodynamic reaction due to generation of inertial waves correctly predicts the trajectory of a descending blob. It also explains the tendency of the plume to develop in the direction intermediate between ${\bm g}_e$ and ${\bm \Omega}$ and to shift ‘eastward’ (lagging the rotation of the centrifuge) if the plume is envisaged as an ensemble of blobs. The stretching of the highly diluted dyed water along the absolute vorticity tubes with simultaneous shearing by horizontal quasi-two-dimensional flow produces conspicuous tilted structures or tilted Taylor ‘ink walls’. The misalignment between ${\bm g}_e$ and ${\bm \Omega}$ enhances the turbulent mixing and development of tilted structures by breaking the symmetry and producing motions directed away from the rotation axis. We argue that the conditions at the sites of ocean deep convection are favourable for the development of tilted structures because of the smallness of the Rossby number and an extreme homogenization of the mixed layer. We hypothesize that the homogenized sublayers observed within actively convecting regions in the ocean may not be horizontal, but in fact analogous to the tilted ‘ink walls’ observed in the laboratory experiments and that they represent the internal structure of a plume on horizontal scales smaller than its depth.
    Description: This work was supported by a grant from The Andrew W. Mellon Foundation Endowed Fund for Innovative Research and by the National Science Foundation grant OCE-0116910.
    Keywords: Convective plumes
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  • 25
    Publication Date: 2022-05-25
    Description: Author Posting. © Cambridge University Press, 2000. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Journal of Fluid Mechanics 404 (2000):117-149, doi:10.1017/S0022112099007065.
    Description: In order to gain insight into the hydraulics of rotating-channel flow, a set of initial-value problems analogous to Long's towing experiments is considered. Specifically, we calculate the adjustment caused by the introduction of a stationary obstacle into a steady, single-layer flow in a rotating channel of infinite length. Using the semigeostrophic approximation and the assumption of uniform potential vorticity, we predict the critical obstacle height above which upstream influence occurs. This height is a function of the initial Froude number, the ratio of the channel width to an appropriately defined Rossby radius of deformation, and a third parameter governing how the initial volume flux in sidewall boundary layers is partitioned. (In all cases, the latter is held to a fixed value specifying zero flow in the right-hand (facing downstream) boundary layer.) The temporal development of the flow according to the full, two-dimensional shallow water equations is calculated numerically, revealing numerous interesting features such as upstream-propagating shocks and separated rarefying intrusions, downstream hydraulic jumps in both depth and stream width, flow separation, and two types of recirculations. The semigeostrophic prediction of the critical obstacle height proves accurate for relatively narrow channels and moderately accurate for wide channels. Significantly, we find that contact with the left-hand wall (facing downstream) is crucial to most of the interesting and important features. For example, no instances are found of hydraulic control of flow that is separated from the left-hand wall at the sill, despite the fact that such states have been predicted by previous semigeostrophic theories. The calculations result in a series of regime diagrams that should be very helpful for investigators who wish to gain insight into rotating, hydraulically driven flow.
    Description: The authors have been supported by the National Science Foundation through Grants (OCE-9810599 for L.J.P. and K.R.H. and OCE-9711186 for EPC). L.J.P. also received support from the Office of Naval Research under Grant N00014-95-1-0456 and K.R.H. under grant N00014-93-1-0263.
    Keywords: Rotating-channel flow ; Hydraulically driven flow
    Repository Name: Woods Hole Open Access Server
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  • 26
    Publication Date: 2022-05-25
    Description: Author Posting. © Cambridge University Press, 2004. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Journal of Fluid Mechanics 514 (2004): 107-119, doi:10.1017/S0022112004000126.
    Description: While acoustic scatter from oceanic turbulence is sensitive to temperature–salinity covariations, there are unfortunately no published measurements of the turbulent temperature–salinity co-spectrum. Several models have been proposed for the form of the co-spectrum of two scalars in turbulence, but they all produce unsatisfactory results when applied to the turbulent scattering equations (either predicting negative scattering cross-sections in some regimes or predicting implausible levels of correlation between temperature and salinity at some scales). A new model is proposed and shown to give physically plausible scattering predictions in all density regimes. High-frequency acoustic data illustrate the importance of the co-spectrum for acoustic scattering, but were collected in a density regime where there is little difference between the co-spectrum models.
    Description: This work was supported by NSERC and by ONR under grant #N00014-93-1-0362.
    Keywords: Oceanic turbulence ; Co-spectrum ; Temperature–salinity covariations
    Repository Name: Woods Hole Open Access Server
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  • 27
    Publication Date: 2022-05-25
    Description: Author Posting. © Cambridge University Press, 2002. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Journal of Fluid Mechanics 452 (2002): 97-121, doi:10.1017/S0022112001006668.
    Description: Buoyancy-driven surface currents were generated in the laboratory by releasing buoyant fluid from a source adjacent to a vertical boundary in a rotating container. Different bottom topographies that simulate both a continental slope and a continental ridge were introduced in the container. The topography modified the flow in comparison with the at bottom case where the current grew in width and depth until it became unstable once to non-axisymmetric disturbances. However, when topography was introduced a second instability of the buoyancy-driven current was observed. The most important parameter describing the flow is the ratio of continental shelf width W to the width L* of the current at the onset of the instability. The values of L* for the first instability, and L*[minus sign]W for the second instability were not influenced by the topography and were 2–6 times the Rossby radius. Thus, the parameter describing the flow can be expressed as the ratio of the width of the continental shelf to the Rossby radius. When this ratio is larger than 2–6 the second instability was observed on the current front. A continental ridge allowed the disturbance to grow to larger amplitude with formation of eddies and fronts, while a gentle continental slope reduced the growth rate and amplitude of the most unstable mode, when compared to the continental ridge topography. When present, eddies did not separate from the main current, and remained near the shelf break. On the other hand, for the largest values of the Rossby radius the first instability was suppressed and the flow was observed to remain stable. A small but significant variation was found in the wavelength of the first instability, which was smaller for a current over topography than over a flat bottom.
    Description: Partial support for C.C. was provided by a TMR fellowship, MAS3-CT96-5017.
    Keywords: Buoyancy-driven currents ; Bottom topography
    Repository Name: Woods Hole Open Access Server
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    facet.materialart.
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    Cambridge University Press
    Publication Date: 2022-05-25
    Description: Author Posting. © Cambridge University Press, 2000. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published Journal of the Marine Biological Association of the UK 80 (2000): 827-834, doi:10.1017/S0025315400002800.
    Description: The shell and internal anatomy of the montacutid bivalve Mysella verrilli is described for the first time. The species is remarkable in that the oesophagus has developed into a suctorial proboscis. This has been accompanied by the loss of the palps. In addition the gonads have been extended from the dorsal part of the body to form two gill-like extensions to which the reduced inner demibranchs attach along the postero–ventral margin. Mysella verrilli broods its young in the mantle cavity to the late veliger stage before releasing them. It is believed that the species is probably a suctorial ectoparasite on a soft-bodied benthic invertebrate.
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  • 29
    Publication Date: 2022-05-25
    Description: Author Posting. © Microscopy Society of America, 2007. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Microscopy and Microanalysis 13 Suppl. 2 (2007): 10-11, doi:10.1017/S1431927607075186.
    Description: Differential interference contrast (DIC) microscopy is widely used to observe structure and motion in unstained, transparent living cells and isolated organelles, producing a monochromatic shadowcast image of optical phase gradient. Polarized light microscopy (Pol) reveals structural anisotropy due to form birefringence, intrinsic birefringence, stress birefringence, etc. DIC and Pol complement each other as, for example, in a live dividing cell, the DIC image will clearly show the chromosomes while the Pol image will depict the distribution of the birefringent microtubules in the spindle. Both methods, however, have the same shortcomings: they require the proper orientation of a specimen in relation to the optical system in order to achieve best results.
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  • 30
    Publication Date: 2022-05-25
    Description: Author Posting. © Cambridge University Press, 2008. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Journal of Fluid Mechanics 604 (2008): 369-388, doi:10.1017/S0022112008001237.
    Description: We discuss laboratory experiments investigating mixing in a density-driven current flowing down a sloping bottom, in a rotating homogenous fluid. A systematic study spanning a wide range of Froude, 0.8 〈 Fr 〈 10, and Reynolds, 10 〈 Re 〈 1400, numbers was conducted by varying three parameters: the bottom slope; the flow rate; and the density of the dense fluid. Different flow regimes were observed, i.e. waves (non-breaking and breaking) and turbulent regimes, while changing the above parameters. Mixing in the density-driven current has been quantified within the observed regimes, and at different locations on the slope. The dependence of mixing on the relevant non-dimensional numbers, i.e. slope, Fr and Re, is discussed. The entrainment parameter, E, was found to be dependent not only on Fr, as assumed in previous studies, but also on Re. In particular, mixing increased with increasing Fr and Re. For low Fr and Re, the magnitude of the mixing was comparable to mixing in the ocean. For large Fr and Re, mixing was comparable to that observed in previous laboratory experiments that exhibited the classic turbulent entrainment behaviour.
    Description: Support was given by the National Science Foundation project number OCE-0350891.
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  • 31
    Publication Date: 2022-05-25
    Description: Author Posting. © Cambridge University Press, 2008. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Journal of Fluid Mechanics 605 (2008): 281-291, doi:10.1017/S002211200800150X.
    Description: A condition is derived for the hydraulic criticality of a 2-layer flow with transverse variations in both layer velocities and thicknesses. The condition can be expressed in terms of a generalized composite Froude number. The derivation can be extended in order to obtain a critical condition for an N-layer system. The results apply to inviscid flows subject to the usual hydraulic approximation of gradual variations along the channel and is restricted to flows in which the velocity remains single-signed within any given layer. For an intermediate layer with a partial segment of sluggish flow, the long-wave dynamics of the overlying and underlying layers become decoupled.
    Description: The work described herein was supported by the Office of Naval Research (N00014- 07-1-0590) and the National Science Foundation (OCE-0525729).
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  • 32
    Publication Date: 2022-05-25
    Description: Author Posting. © Cambridge University Press, 2008. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Journal of Fluid Mechanics 616 (2008): 327-356, doi:10.1017/S0022112008003984.
    Description: A steady theory is presented for gravity currents propagating with constant speed into a stratified fluid with a general density profile. Solution curves for front speed versus height have an energy-conserving upper bound (the conjugate state) and a lower bound marked by the onset of upstream influence. The conjugate state is the largest-amplitude nonlinear internal wave supported by the ambient stratification, and in the limit of weak stratification approaches Benjamin's energy-conserving gravity current solution. When the front speed becomes critical with respect to linear long waves generated above the current, steady solutions cannot be calculated, implying upstream influence. For non-uniform stratification, the critical long-wave speed exceeds the ambient long-wave speed, and the critical-Froude-number condition appropriate for uniform stratification must be generalized. The theoretical results demonstrate a clear connection between internal waves and gravity currents. The steady theory is also compared with non-hydrostatic numerical solutions of the full lock release initial-value problem. Some solutions resemble classic gravity currents with no upstream disturbance, but others show long internal waves propagating ahead of the gravity current. Wave generation generally occurs when the stratification and current speed are such that the steady gravity current theory fails. Thus the steady theory is consistent with the occurrence of either wave-generating or steady gravity solutions to the dam-break problem. When the available potential energy of the dam is large enough, the numerical simulations approach the energy-conserving conjugate state. Existing laboratory experiments for intrusions and gravity currents produced by full-depth lock exchange flows over a range of stratification profiles show excellent agreement with the conjugate state solutions.
    Description: K. R. H. was supported by ONR grant N000140610798
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  • 33
    Publication Date: 2022-05-25
    Description: Author Posting. © Cambridge University Press, 2002. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Journal of Fluid Mechanics 468 (2002): 179-204, doi:10.1017/S0022112002001520.
    Description: A similarity solution to the long-wave shallow-water equations is obtained for a density current (reduced gravity = g[prime prime or minute], Coriolis parameter = f) propagating alongshore (y = 0). The potential vorticity q = f/H1 is uniform in [minus sign][infty infinity] 〈 x [less-than-or-eq, slant] xnose(t), 0 〈 y [less-than-or-eq, slant] L(x, t), and the nose of this advancing potential vorticity front displaces fluid of greater q = f/H0, which is located at L 〈 y 〈 [infty infinity]. If L0 = L([minus sign][infty infinity], t), the nose point with L(xnose(t), t) = 0 moves with velocity Unose = [surd radical]g[prime prime or minute]H0 [phi], where [phi] is a function of H1/H0, f2L20/g[prime prime or minute]H0. The assumptions made in the similarity theory are verified by an initial value solution of the complete reduced-gravity shallow-water equations. The latter also reveal the new effect of a Kelvin shock wave colliding with a potential vorticity front, as is confirmed by a laboratory experiment. Also confirmed is the expansion wave structure of the intrusion, but the observed values of Unose are only in qualitative agreement; the difference is attributed to the presence of small-scale (non-hydrostatic) turbulence in the laboratory experiment but not in the numerical solutions.
    Description: This work is funded by National Science Foundation grants OCE-9726584 & OCE-0092504 (M. E. S.) and OCE-9810599 (K. R. H.).
    Keywords: Potential vorticity front ; Frontal intrusion ; Kelvin wave
    Repository Name: Woods Hole Open Access Server
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  • 34
    Publication Date: 2022-05-25
    Description: Author Posting. © Cambridge University Press, 2003. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Journal of Fluid Mechanics 481 (2003): 329-353, doi:10.1017/S0022112003004051.
    Description: In this article we investigate time-periodic shear flows in the context of the two-dimensional vorticity equation, which may be applied to describe certain large-scale atmospheric and oceanic flows. The linear stability analyses of both discrete and continuous profiles demonstrate that parametric instability can arise even in this simple model: the oscillations can stabilize (destabilize) an otherwise unstable (stable) shear flow, as in Mathieu's equation (Stoker 1950). Nonlinear simulations of the continuous oscillatory basic state support the predictions from linear theory and, in addition, illustrate the evolution of the instability process and thereby show the structure of the vortices that emerge. The discovery of parametric instability in this model suggests that this mechanism can occur in geophysical shear flows and provides an additional means through which turbulent mixing can be generated in large-scale flows.
    Description: F.P.’s and G.F.’s research was supported by grants from NSF, OPP- 9910052 and OCE-0137023. J.P.’s research is supported in part by a grant from NSF, OCE-9901654.
    Keywords: Time-periodic shear flows ; Parametric instability
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  • 35
    Publication Date: 2022-05-25
    Description: Author Posting. © Cambridge University Press, 2004. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Journal of Fluid Mechanics 515 (2004): 415-443, doi:10.1017/S0022112004000576.
    Description: The investigation involves the hydraulic behaviour of a dense layer of fluid flowing over an obstacle and subject to entrainment of mass and momentum from a dynamically inactive (but possibly moving) overlying fluid. An approach based on the use of reduced gravity, shallow-water theory with a cross-interface entrainment velocity is compared with numerical simulations based on a model with continuously varying stratification and velocity. The locations of critical flow (hydraulic control) in the continuous model are estimated by observing the direction of propagation of small-amplitude long-wave disturbances introduced into the flow field. Although some of the trends predicted by the shallow-water model are observed in the continuous model, the agreement between the interface profiles and the position of critical flow is quantitatively poor. A reformulation of the equations governing the continuous flow suggests that the reduced gravity model systematically underestimates inertia and overestimates buoyancy. These differences are quantified by shape coefficients that measure the vertical non-uniformities of the density and horizontal velocity that arise, in part, by incomplete mixing of entrained mass and momentum over the lower-layer depth. Under conditions of self-similarity (as in Wood's similarity solution) the shape coefficients are constant and the formulation determines a new criterion for and location of critical flow. This location generally lies upstream of the critical section predicted by the reduced-gravity model. Self-similarity is not observed in the numerically generated flow, but the observed critical section continues to lie upstream of the location predicted by the reduced gravity model. The factors influencing this result are explored.
    Description: M. H. N. would like to thank the Danish Natural Science Research Council for financial support. L. P. and K. H. were supported by the Office of Naval Research under grant N00014-1-01-0167 and by the National Science Foundation under grant OCE-0132903.
    Keywords: Hydraulic behaviour ; Reduced gravity model
    Repository Name: Woods Hole Open Access Server
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    Cambridge University Press
    Publication Date: 2022-05-25
    Description: Author Posting. © Cambridge University Press, 2001. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Journal of Fluid Mechanics 437 (2001): 301-323, doi:10.1017/S0022112001004402.
    Description: Laboratory and numerical experiments are used to study flow of a uniform-density fluid on the [beta]-plane around a thin zonally elongated island (or ridge segment in the abyss). This orientation is chosen specifically to highlight the roles of the zonal boundary layer dynamics in controlling the circulation around the island. There are examples of deep ocean topography that fall into this category which make the work directly applicable to oceanic flows. Linear theory for the transport around the island and the flow structure is based on a modification of the Island Rule (Pedlosky et al. 1997; Pratt & Pedlosky 1999). The linear solution gives a north–south symmetric flow around the island with novel features, including stagnation points which divide the zonal boundary layers into eastward and westward flowing zones, and a western boundary layer of vanishing length, and zonal jets. Laboratory experiments agree with the linear theory for small degrees of nonlinearity, as measured by the ratio of the inertial to Munk boundary layer scales. With increasing nonlinearity the north–south symmetry is broken. The southern stagnation point (for anticyclonic forcing) moves to the eastern tip of the island. The flow rounding the eastern tip from the northern side of the island now separates from the island. Time-dependence emerges and recirculation cells develop on the northern side of the island. Mean transport around the island is relatively unaffected by nonlinearity and given to within 20% by the modified Island Rule. Numerical solutions of the shallow water equations are in close agreement with the laboratory results. The transition from zonal to meridional island orientation occurs for island inclinations from zonal greater than about 20°.
    Description: This work was supported by the National Science Foundation (Grant Number OCE96-16949).
    Keywords: Zonal boundary layer dynamics ; Island Rule
    Repository Name: Woods Hole Open Access Server
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  • 37
    Publication Date: 2022-05-25
    Description: Author Posting. © Cambridge University Press, 2006. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Journal of Fluid Mechanics 564 (2006): 435-454, doi:10.1017/S0022112006001522.
    Description: Motivated by work on tilted convection (Sheremet, J. Fluid Mech., vol. 506, 2004, p. 217), a set of experiments is presented here using the same set-up of a tilted tank attached to a rotating centrifuge with a 2.5 m arm. Within the tank small, almost neutrally buoyant, spheres are released, and their trajectories are recorded. Thus the forces acting on a sphere can be analysed in the case of misalignment between the buoyancy force and the axis of rotation. The angles of descent characterizing the trajectory are compared with inviscid linear theory developed by Stewartson (Q. J. Math. Appl. Mech., vol. 6, 1953, p. 141), and the agreement is found to be good. The angles should be independent of the density anomaly of the spheres compared to their environment. Using the descent velocity from non-rotating experiments, the density of the spheres is estimated and used to determine the drag acting on them in the rotating experiments. It is found that the drag is up to 50% larger than expected from Stewartson's theory. The agreement is best, not for infinitesimal, but for small Rossby numbers. The results are consistent with observations recorded by Maxworthy (J. Fluid Mech., vol. 40, 1970, p. 453).
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  • 38
    Publication Date: 2022-05-25
    Description: Author Posting. © Cambridge University Press, 2007. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Journal of Fluid Mechanics 593 (2007): 1-32, doi:10.1017/S0022112007008415.
    Description: Results are presented from an experimental study of shallow flow in a channel partially obstructed by an array of circular cylinders. The cylinder array is a model for emergent vegetation in an open channel, but also represents a simple sparse porous medium. A shear layer with regular vortex structures forms at the edge of the array, evolving downstream to an equilibrium width and vortex size. The vortices induce nearly periodic oscillations with a frequency that matches the most unstable linear mode for a parallel shear flow. The shear layer is asymmetric about the array interface and has a two-layer structure. An inner region of maximum shear near the interface contains a velocity inflection point and establishes the penetration of momentum into the array. An outer region, resembling a boundary layer, forms in the main channel, and establishes the scale of the vortices. The vortex structure, educed by conditional sampling, shows strong crossflows with sweeps from the main channel and ejections from the array, which create significant momentum and mass fluxes across the interface. The sweeps maintain the coherent structures by enhancing shear and energy production at the interface. A linear stability analysis is consistent with the experimental results and demonstrates that the instability is excited by the differential drag between the channel and the array.
    Description: This material is based upon work supported by the National Science Foundation under Grant 0125056.
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  • 39
    Publication Date: 2022-05-26
    Description: Author Posting. © Cambridge University Press, 2005. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Journal of Fluid Mechanics 536 (2005): 253-283, doi:10.1017/S0022112005004544.
    Description: The generation of a gravity current by the release of a semi-infinite region of buoyant fluid of depth $H$ overlying a deeper, denser and quiescent lower layer in a rotating channel of width $w$ is considered. Previous studies have focused on the characteristics of the gravity current head region and produced relations for the gravity current speed $c_{b}$ and width $w_b$ as a functions of the local current depth along the wall $h_b$, reduced gravity $g^\prime$, and Coriolis frequency $f$. Here, the dam-break problem is solved analytically by the method of characteristics assuming reduced-gravity flow, uniform potential vorticity and a semigeostrophic balance. The solution makes use of a local gravity current speed relation $c_{b} \,{=}\, c_b(h_b,\ldots)$ and a continuity constraint at the head to close the problem. The initial value solution links the local gravity current properties to the initiating dam-break conditions. The flow downstream of the dam consists of a rarefaction joined to a uniform gravity current with width $w_b$ (${\le}\, w$) and depth on the right-hand wall of $h_b$, terminated at the head moving at speed $c_b$. The solution gives $h_b$, $c_b$, $w_b$ and the transport of the boundary current as functions of $w/L_R$, where $L_R \,{=}\, \sqrt{g^\prime H}/f$ is the deformation radius. The semigeostrophic solution compares favourably with numerical solutions of a single-layer shallow-water model that internally develops a leading bore. Existing laboratory experiments are re-analysed and some new experiments are undertaken. Comparisons are also made with a three-dimensional shallow-water model. These show that lateral boundary friction is the primary reason for differences between the experiments and the semigeostrophic theory. The wall no-slip condition is identified as the primary cause of the experimentally observed decrease in gravity current speed with time. A model for the viscous decay is developed and shown to agree with both experimental and numerical model data.
    Description: This work was supported by NSF Grants OCE-0095059 and OCE-0132903.
    Keywords: Gravity current ; Dam-break problem
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  • 40
    Publication Date: 2022-05-26
    Description: Author Posting. © Cambridge University Press, 2006. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Journal of Fluid Mechanics 561 (2006):103–112, doi:10.1017/S0022112006000991
    Description: A self-consistent formalism to estimate baroclinic energy densities and fluxes resulting from the propagation of internal waves of arbitrary amplitude is derived using the concept of available potential energy. The method can be applied to numerical, laboratory or field data.
    Description: MBIWE98 was supported by the US Geological Survey and the Office of Naval Research. A.S. received support from the Office of Naval Research (N00014-05-1-0361), R.B. from the Walter A. and Hope Noyes Smith Chair on Coastal Oceanography and B.B. from the US Geological Survey.
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  • 41
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    Cambridge University Press
    Publication Date: 2022-05-26
    Description: Author Posting. © Cambridge University Press, 2003. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Journal of Fluid Mechanics 490 (2003): 189-215, doi:10.1017/S0022112003005007.
    Description: The baroclinic instability of a zonal current on the beta-plane is studied in the context of the two-layer model when the shear of the basic current is a periodic function of time. The basic shear is contained in a zonal channel and is independent of the meridional direction. The instability properties are studied in the neighbourhood of the classical steady-shear threshold for marginal stability. It is shown that the linear problem shares common features with the behaviour of the well-known Mathieu equation. That is, the oscillatory nature of the shear tends to stabilize an otherwise unstable current while, on the contrary, the oscillation is able to destabilize a current whose time-averaged shear is stable. Indeed, this parametric instability can destabilize a flow that at every instant possesses a shear that is subcritical with respect to the standard stability threshold. This is a new source of growing disturbances. The nonlinear problem is studied in the same near neighbourhood of the marginal curve. When the time-averaged flow is unstable, the presence of the oscillation in the shear produces both periodic finite-amplitude motions and aperiodic behaviour. Generally speaking, the aperiodic behaviour appears when the amplitude of the oscillating shear exceeds a critical value depending on frequency and dissipation. When the time-averaged flow is stable, i.e. subcritical, finite-amplitude aperiodic motion occurs when the amplitude of the oscillating part of the shear is large enough to lift the flow into the unstable domain for at least part of the cycle of oscillation. A particularly interesting phenomenon occurs when the time-averaged flow is stable and the oscillating part is too small to ever render the flow unstable according to the standard criteria. Nevertheless, in this regime parametric instability occurs for ranges of frequency that expand as the amplitude of the oscillating shear increases. The amplitude of the resulting unstable wave is a function of frequency and the magnitude of the oscillating shear. For some ranges of shear amplitude and oscillation frequency there exist multiple solutions. It is suggested that the nature of the response of the finite-amplitude behaviour of the baroclinic waves in the presence of the oscillating mean flow may be indicative of the role of seasonal variability in shaping eddy activity in both the atmosphere and the ocean.
    Description: J.P.’s research is supported in part by a grant from NSF, OCE 9901654.
    Keywords: Baroclinic instability ; Baroclinic waves
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  • 42
    Publication Date: 2022-05-26
    Description: Author Posting. © Cambridge University Press, 2000. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Zygote 8 (2000): 15-24, doi:10.1017/S0967199400000782.
    Description: The physiology of the early embryo may be indicative of embryo vitality and therefore methods for non-invasively monitoring physiological parameters from embryos could improve preimplantation diagnoses. The self-referencing electrophysiological technique is capable of non-invasive measurement of the physiology of individual cells by monitoring the movement of ions and molecules between the cell and the surrounding media. Here we use this technique to monitor gradients of calcium, potassium, oxygen and hydrogen peroxide around individual mouse preimplantation embryos. The calcium-sensitive electrode in self-referencing mode identified a region of elevated calcium concentration ([similar]0.25 pmol) surrounding each embryo. The calcium gradient surrounding embryos was relatively steep, such that the region of elevated calcium extended into the medium only 4 [mu]m from the embryo. By contrast, using an oxygen-sensitive electrode an extensive gradient of reduced dissolved oxygen concentration was measured surrounding the embryo and extended tens of micrometres into the medium. A gradient of neither potassium nor hydrogen peroxide was observed around unperturbed embryos. We also demonstrate that monitoring the physiology of embryos using the self-referencing technique does not compromise their subsequent development. Blastocysts studied with the self-referencing technique implanted and developed to term at the same frequency as did unexamined, control embryos. Therefore, the self-referencing electrode provides a valuable non-invasive technique for studying the physiology and pathophysiology of individual embryos without hindering their subsequent development.
    Description: A portion of this work was funded by an NIH R21 #RR 12718–02 to D.L.K. and P.J.S.S., KO81099 to D.L.K. and NIH P41 RR01395 to P.J.S.S.
    Keywords: Calcium ; Embryo physiology ; Embryo transfer ; Oxygen ; Preimplantation diagnosis
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  • 43
    facet.materialart.
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    Cambridge University Press
    Publication Date: 2022-05-26
    Description: Author Posting. © Cambridge University Press, 2005. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Journal of Fluid Mechanics 529 (2005): 71-95, doi:10.1017/S0022112005003393.
    Description: The role of mesoscale oceanic eddies in driving large-scale currents is studied in an eddy-resolving midlatitude double-gyre ocean model. The reference solution is decomposed into large-scale and eddy components in a way which is dynamically consistent with a non-eddy-resolving ocean model. That is, the non-eddy-resolving solution driven by this eddy-forcing history, calculated on the basis of this decomposition, correctly approximates the original flow. The main effect of the eddy forcing on the large-scale flow is to enhance the eastward-jet extension of the subtropical western boundary current. This is an anti-diffusive process, which cannot be represented in terms of turbulent diffusion. It is shown that the eddy-forcing history can be approximated as a space–time correlated, random-forcing process in such a way that the non-eddy-resolving solution correctly approximates the reference solution. Thus, the random-forcing model can potentially replace the diffusion model, which is commonly used to parameterize eddy effects on the large-scale currents. The eddy-forcing statistics are treated as spatially inhomogeneous but stationary, and the dynamical roles of space–time correlations and spatial inhomogeneities are systematically explored. The integral correlation time, oscillations of the space correlations, and inhomogeneity of the variance are found to be particularly important for the flow response.
    Description: Funding for this research was provided by NSF grants OCE 0091836 and OCE 03-44094, by the Royal Society Fellowship, and by WHOI grants 27100056 and 52990035.
    Keywords: Mesoscale oceanic eddies ; Large-scale currents ; Random-forcing model
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  • 44
    Publication Date: 2022-05-26
    Description: Author Posting. © Cambridge University Press, 2002. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Journal of Fluid Mechanics 464 (2002): 251-278, doi:10.1017/S0022112002008868.
    Description: The dynamics of buoyant gravity currents in a rotating reference frame is a classical problem relevant to geophysical applications such as river water entering the ocean. However, existing scaling theories are limited to currents propagating along a vertical wall, a situation almost never realized in the ocean. A scaling theory is proposed for the structure (width and depth), nose speed and flow field characteristics of buoyant gravity currents over a sloping bottom as functions of the gravity current transport Q, density anomaly g[prime prime or minute], Coriolis frequency f, and bottom slope [alpha]. The nose propagation speed is cp [similar] cw/ (1 + cw/c[alpha]) and the width of the buoyant gravity current is Wp [similar] cw/ f(1 + cw/c[alpha]), where cw = (2Qg[prime prime or minute] f)1/4 is the nose propagation speed in the vertical wall limit (steep bottom slope) and c[alpha] = [alpha]g/f is the nose propagation speed in the slope-controlled limit (small bottom slope). The key non-dimensional parameter is cw/c[alpha], which indicates whether the bottom slope is steep enough to be considered a vertical wall (cw/c[alpha] [rightward arrow] 0) or approaches the slope-controlled limit (cw/c[alpha] [rightward arrow] [infty infinity]). The scaling theory compares well against a new set of laboratory experiments which span steep to gentle bottom slopes (cw/c[alpha] = 0.11–13.1). Additionally, previous laboratory and numerical model results are reanalysed and shown to support the proposed scaling theory.
    Description: This research was supported by NSF grant OCE-0095059.
    Keywords: Buoyant gravity currents ; Scaling theory ; Sloping bottom
    Repository Name: Woods Hole Open Access Server
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  • 45
    Publication Date: 2022-05-26
    Description: Author Posting. © Cambridge University Press, 2003. This article is posted here by permission of Cambridge University Press for personal use, not for redistribution. The definitive version was published in Journal of the Marine Biological Association of the UK 83 (2003): 1347-1350, doi:10.1017/S0025315403008798.
    Description: Trophic positions (TP) were estimated for the blue shark (Prionace glauca), shortfin mako (Isurus oxyrinchus), thresher shark (Alopias vulpinus), and basking shark (Cetorhinus maximus) using stable isotope ratios of carbon ([delta]13C) and nitrogen ([delta]15N). The basking shark had the lowest TP (3·1) and [delta]15N value (10·4‰), whereas the thresher shark had the highest values (4·5, 15·2‰). Mako sharks showed considerable variation in TP and isotopic values, possibly due to foraging from both inshore and offshore waters. Thresher sharks were significantly more enriched in [delta]15N than blue sharks and mako sharks, suggesting a different prey base. The [delta]13C values of thresher sharks and mako sharks varied significantly, but neither was significantly different from that of blue sharks. No statistical differences were found between our TP estimations and those derived from published stomach contents analyses, indicating that stable isotope data may be used to estimate the trophic status of sharks.
    Description: This work was supported by National Marine Fisheries Service Grant NA16MF1323 to M.E.L.
    Keywords: Prionace glauca ; Isurus oxyrinchus ; Alopias vulpinus ; Cetorhinus maximus ; Trophic positions
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  • 46
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    Cambridge University Press
    In:  Biased embryos and evolution vol. 74, 1/2, pp. 209-211
    Publication Date: 2024-01-12
    Keywords: evolution ; natural selection ; variation ; developmental bias
    Repository Name: National Museum of Natural History, Netherlands
    Type: info:eu-repo/semantics/review
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  • 47
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    The Journal of Chemical Physics 91 (1989), S. 4455-4461 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Intermolecular potentials for Ar and Kr interacting with HBr are obtained by least-squares fitting of potential parameters to data obtained from the molecular-beam microwave spectra of the Ar–HBr and Kr–HBr van der Waals complexes. The equilibrium geometry is linear Rg–H–Br in each case, but there are substantial secondary minima at the linear Rg–Br–H geometries; for Ar–HBr, the secondary minimum is only about 5 cm−1 shallower than the primary minimum. This potential feature is found to explain the anomalous H/D isotope effects in centrifugal distortion constants that have been observed for the Rg–HBr complexes. It is predicted that Ar–HBr will have a very low-energy bending state, only 11 cm−1 above the ground state, arising from the secondary minimum.
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  • 48
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    The Journal of Chemical Physics 91 (1989), S. 4477-4484 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Excited rotational level dependence of the external magnetic field effects both on intensity and on decay of fluorescence of pyrazine vapor has been carefully examined for the zero-point vibrational level in S1 with a field strength of 0–170 G. The magnetic quenching of the slow fluorescence becomes more effective with increasing rotational quantum number J' of the excited level, and the field strength at which the amount of fluorescence quenching becomes one-half of the total amount of quenching at the saturated fields is roughly proportional to (2J'+1)−1. The magnetic quenching is also found to depend on K' of the excited level. The rotational level dependence of the magnetic quenching of the slow fluorescence is related to a difference in the number of the triplet levels coupled to the optically excited singlet rovibronic level, based on the spin decoupling mechanism of the singlet–triplet mixed level.
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  • 49
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    The Journal of Chemical Physics 91 (1989), S. 4499-4503 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: We have observed many collision-induced-dipole (CID) absorption bands arising from the transitions between quasimolecular ground and high-lying (n≤10) states in the strontium–rare-gas systems. For each absorption band, we have measured the energy shift of the absorption peak from the energy of the correlating atomic forbidden transition and the effective oscillator strength per unit perturber density fCID/Np. The shift is roughly proportional to the electron scattering length L0 for each rare-gas atom, whereas the fCID/Np is roughly proportional to L20. The shift decreases in general as the principal quantum number n increases, and increases as one goes from the s state to the d state, and to the degenerate manifold state with l≥3. These general features of the shift and fCID/Np are consistent with the predictions by a simple Fermi-potential model, suggesting the important role of the interaction between a Rydberg electron and a rare-gas atom in the CID absorption processes.
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  • 50
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    The Journal of Chemical Physics 91 (1989), S. 4582-4586 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The ν2 band of the silylene SiH2 molecule in X˜ 1 A1 was observed for the first time in the gas phase by using infrared diode laser kinetic spectroscopy. Silylene molecules were generated by the photolysis of phenylsilane at 193 nm. The observed spectrum was analyzed to determine the rotational and centrifugal distortion constants in the ground and v2 =1 states and the band origin ν0 =998.6241(3) cm−1 with one standard deviation in parentheses. The significance of the derived parameters is discussed in detail.
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  • 51
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    The Journal of Chemical Physics 91 (1989), S. 4597-4602 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Using translational spectroscopy we have studied the d 1Πg and C 3 Πg Rydberg states of O2 . The dissociation of the vibrational levels v=0–2 to all energetically accessible dissociation limits has been followed. The dissociation pathways directly reflect the predissociation mechanisms involved. For the d 1 Πg Rydberg state competition between predissociation by a 3 Πg valence state, due to singlet–triplet mixing, and by a 1 Πg valence state has been observed. Using the Fermi golden rule the observed vibrationally dependent competition is reproduced, corroborating the positions of the lower 1 Πg and 3 Πg valence state curves and yielding various coupling strengths.
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  • 52
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    The Journal of Chemical Physics 91 (1989), S. 4636-4642 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Rotationally inelastic scattering of carbon dioxide by translationally hot H, D, and Cl atoms was studied by time-resolved diode laser absorption. The high J rotational distribution falls off quite rapidly between J=60 and J=80. D atom collisions have roughly twice the excitation cross section versus H atom collisions, with the H*/D* ratio decreasing with increasing J. These results are consistent with a constraint on the total reagent orbital angular momentum available for rotational excitation. Transient Doppler profiles measured immediately after hot atom/CO2 collisions indicate that CO2 molecules excited to high J levels have a larger recoil velocity than molecules excited to lower J levels. This result is consistent with predictions based on a simple model which treats the CO2 potential as a hard shell ellipsoid.
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    The Journal of Chemical Physics 91 (1989), S. 4643-4650 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The molecular dynamics simulation method is extended to study a model of diffusion-controlled reactions. This allows a molecular description of solvent at an equal footing of reactants. Nondiffusional dynamic behavior of reactive molecules is found at short times. It enhances the rate of reactive encounter in comparison to the prediction of Smoluchowski theory. The model studied in this work can be regarded as a theoretical prototype of fluorescence quenching. In this context it is shown that the nondiffusional dynamics is mainly responsible for the discrepancy between Stern–Volmer plots measured in a continuous excitation experiment or obtained by integrating the time resolved fluorescence intensity. The other aspects such as the long-time behavior of survival probability, solvent effect as well as competing effect from finite concentration of one reactive species are also studied in some detail.
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  • 54
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    The Journal of Chemical Physics 91 (1989), S. 4714-4727 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The reactions of neutral iron clusters Fe7–27 with water are studied in a laser-vaporization cluster source coupled to a continuous-flow reactor. Reaction products are detected via laser ionization and time-of-flight mass spectrometry. The reactions of room-temperature clusters with H2O show adsorbate decomposition and hydrogen desorption, as do the reactions with D2O at elevated temperatures. The room-temperature reaction with D2O appears not to involve any decomposition, and is at equilibrium under the conditions of these experiments. The dependence of reaction extent on D2O pressure yields equilibrium constants for the addition of the first and second D2O molecules. The analysis is complicated by the presence of two-photon ionization processes that are treated quantitatively with a rate-equation model. This treatment also yields estimates for cluster photoabsorption cross sections, which are found to be approximately linear in cluster size, having a magnitude of 2.3×10−17 cm2 per iron atom. From the derived equilibrium constants and estimated adsorption entropies, approximate D2O–cluster binding energies are determined. They range from 0.42 to 0.59 eV, and their dependence on cluster size shows a remarkable similarity to the dependence of the rate constants for reaction of iron clusters with H2. The implications of this similarity are discussed.
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    The Journal of Chemical Physics 91 (1989), S. 4738-4744 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Relativistic effect Erel upon the total electronic energy of an atom is discussed with particular reference to obtaining the nonrelativistic total energy Eexact from the experimental total energy. Numerical values of this effect obtained by various authors by different nonempirical methods are compared for neutral atoms of rare-gas elements. It is shown that methods either of a Hartree–Fock-type or of a Dirac–Hartree–Fock-type give much the same Erel value for He through Ar. It is pointed out that Erel calculated with Hartree–Fock wave functions is not adequate for use in obtaining Eexact from the experimental total energy and that the Erel value calculated with wave functions including electron correlation should work well, although an actual demonstration can be done only for two-electron systems for lack of data. A semiempirical formula is therefore proposed, which is useful for least-squares fit of experimental total energies of isoelectronic series of atoms to extract nonrelativistic total energies along with the relativistic effect. From nonrelativistic energies thus derived, semiempirical values of correlation energies of atoms are obtained. The results thus obtained are in reasonable agreement with correlation energies derived by Clementi along somewhat different lines. The power series expansion in Z of the fitted formula for the He series shows that numerical values of expansion coefficients agree reasonably well with the corresponding values obtained by accurate relativistic and nonrelativistic Z expansion-type calculations.
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  • 56
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    The Journal of Chemical Physics 91 (1989), S. 4785-4792 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The ground and low-lying states of CuF2 and CuCl2 have been studied using the single and doubles configuration interaction (SDCI) and coupled pair functional (CPF) methods in a large Gaussian basis set including up to g-type functions. The results include a determination of the bond distances for all the ligand field states (the three states with one hole in the 3d shell) and charge transfer (CT) states, and force constants for the ligand field states. Overall the SDCI (with or without the Davidson correction for higher excitations) and CPF results are in good agreement. The CPF results, which we believe to be the most accurate, can be summarized as follows. The computed value for the asymmetric stretching frequency in the 2Σ+g ground state of CuF2 is 740 cm−1, compared to the experimental value of 765 cm−1. The d–d transition energies for CuF2 are 2500 and 10 800 cm−1. The two lowest charge transfer states are at 31 200 and 33 900 cm−1, respectively. CuCl2 has been found to have a ground state which is an almost equal mixture of 2Σ+g and 2Πg when an estimate of the spin–orbit interaction is included. Three d–d transitions are found: 1600 cm−1 ( J=1/2), 7500 cm−1 (J=3/2), and 9700 cm−1 (J=5/2). The lowest charge transfer states have been computed to lie at 16 700 and 19 600 cm−1. Two bands have been found in the gas-phase spectrum of CuCl2 at 9000 and 19 000 cm−1, in good agreement with the present results. The computed f value for the CT band is 0.017, to be compared to the experimental value of 0.014.
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    The Journal of Chemical Physics 91 (1989), S. 4909-4911 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The dissociation equilibrium AlBr=Al+Br was studied by effusion beam mass spectrometry over the range 1970 to 2260 K and the dissociation energy D00(AlBr) was derived as 4.41±0.06 eV. This value is in general agreement with other fragmentary thermochemical results, but it is lower than a value derived from a short extrapolation of vibrational levels in the excited 1π state, doubtless because of a potential maximum of about 0.22 eV in that state. A Birge–Sponer extrapolation of the ground state vibrational levels, when corrected for degree of ionicity, yields a D00 value in close accord with the experimental result, but an electrostatic model calculation falls short by 0.45 eV.
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    The Journal of Chemical Physics 91 (1989), S. 4920-4925 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: A new scheme of experimental criterion is proposed for estimating the carrier mobility and main-chain conformation of an electroactive polymer chain by the technique of transient electric birefringence (TEB). The rise response Δnr (t) and the decay response Δnd (t) in the TEB satisfy in the Kerr regime (i) Δnr (t)=Δnst -Δnd (t) for a polymer molecule of arbitrary conformation with an induced dipole moment alone arising from carriers highly mobile along the main chain, (ii) Δnr (t)=Δnst -(3/2)Δnd (t/3)+(1/2)Δnd (t) for a rodlike polymer molecule with a permanent dipole moment alone originating from carriers with low mobility, and (iii) Δnr(t)=Δnst-2Δnd (t/2)+Δnd (t) for a random-coiled polymer with a permanent dipole moment alone due to low-mobility carriers, where Δnst =limt→∞ Δnr(t) . Then, comparison of the TEB rise and decay responses gives us information on the carrier mobility and main-chain conformation. This criterion is valid also for polydispersed polymer samples. By applying the criterion to the exemplifying data of the TEB responses for soluble urethane-substituted polydiacetylenes, it is found that the polydiacetylene molecules take a random-coil conformation with a permanent dipole moment in a good solvent, while in a poor solvent the carrier mobility depends crucially on the solvent condition.
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    The Journal of Chemical Physics 91 (1989), S. 4942-4948 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The rate of catalytic carbon monoxide oxidation on a Pt(100) single crystal surface under isothermal, low-pressure conditions exhibits for certain ranges of parameters (O2 and CO partial pressures, temperature) sustained temporal oscillations whose mechanism had been explored in previous work. Coupling between reaction and diffusion leads to spatial pattern formation as manifested by patches with different work function on the intrinsically homogeneous surface. Imaging is performed by means of the novel technique of scanning photoemission microscopy. Typically, nuclei with dimensions of a few microns, as determined by the instrumental resolution, are formed spontaneously and expand with sharp fronts and velocities of about 0.5 mm/min (at 480 K) up to sizes ≥1 mm. Waves with even more extended fronts propagating with somewhat higher velocities across the sample surface are responsible for the occurrence of large amplitude temporal oscillations of the integral reaction rate.
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    The Journal of Chemical Physics 91 (1989), S. 4338-4345 
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    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Carbon K edge near edge x-ray absorption fine structure (NEXAFS) spectra of adsorbed acetonitrile and reactive intermediates derived therefrom on Ag(110) were studied in order to determine their orientation and bonding to the surface. For both the multilayer and the adsorbed monolayer there is excellent agreement between the spectra of the adsorbed acetonitrile and the gas phase species. For the multilayer coverage the orientation of the acetonitrile molecules is not completely random; the molecules prefer an orientation with their bond axes closer to parallel than perpendicular to the surface. At monolayer coverage acetonitrile bound to the surface is unrehybridized. It is bound with its linear molecular skeleton parallel to the surface and randomly oriented azimuthally. Annealing molecular CH3 CN to 325 K in the presence of coadsorbed atomic oxygen produces a linear CH2 CN surface intermediate, the molecular axis of which is parallel to the surface and perpendicular to the close-packed direction. The C–C and C–N bond lengths are essentially unperturbed from their values in gas phase CH3 CN. Bonding appears to occur between the methylene carbon and the metal, as expected. A broadening of the π* resonance for transition into the π* orbital perpendicular to the surface is interpreted in terms of π-donor bonding.
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    The Journal of Chemical Physics 91 (1989), S. 4265-4272 
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    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Attenuated total reflectance (ATR) from principal faces of orthorhombic (and higher symmetry) crystals in spectral regions including strongly polar optic modes is considered. A detailed, quantitative comparison between experimental and calculated ATR infrared (IR) spectra of orthorhombic sodium nitroprusside dihydrate (SNP), Na2[Fe(CN)5NO]⋅2H2O, single crystals in the 500–3800 cm−1 region is presented. Calculated ATR spectra are generated employing the dielectric tensor of SNP obtained from Kramers–Kronig analysis of external reflectance data. The dependence of intensities, profiles, and locations of bands in the spectra upon the relative refractive index of the sample against the ATR prism and the polarization state of the reflected IR beam will be discussed. Both theoretical and experimental evidence of the coupling of the TM-polarized evanescent wave with strong in-plane-polarized optic modes at about their LO frequencies will be given with reference to the case of the strong NO stretching mode of SNP. Finally, the computed and experimental ATR results in SNP single crystals will be critically compared with powder ATR data and reported polarized IR transmittance spectra of SNP single crystals plates.
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    The Journal of Chemical Physics 91 (1989), S. 4299-4306 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: X-ray diffraction data for liquid n-butane near the triple and boiling points are presented. The data are analyzed using scattering factors for −CH3 and −CH2 groups which permits extraction of structure and distribution functions for carbon sites. An intramolecular carbon–carbon distance at approximately 3.1 A(ring) is assigned to a short end-to-end distance in a near-gauche conformation, which is in agreement with the electron diffraction results for gaseous n-butane. The intermolecular pair distribution functions show a large difference in the liquid structure for the low and high temperature states, similar to that found in liquid propane.
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    The Journal of Chemical Physics 91 (1989), S. 4330-4337 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We report studies of the kinetics of thermal desorption of In from Ga-stabilized GaAs(100) in ultrahigh vacuum. The relative coverage of In was monitored by x-ray photoelectron spectroscopy (XPS), while the substrate temperature was accurately measured using infrared laser interferometric thermometry. The In was deposited on GaAs by dosing, at room temperature, to saturated monolayer coverage with trimethylindium, yielding In ∼2×1014 cm−2. Subsequent heating to 400 °C desorbs all hydrocarbon species without affecting the In coverage. Further heating leads to first-order desorption of In, as confirmed by exponential decay of In(3d 5/2) XPS signal in isothermal desorption experiments at 473 and 503 °C. From temperature programmed desorption studies through the range 450 to 530 °C, differentiation of the In coverage vs time yielded desorption rates from which Arrhenius parameters were extracted. The unit-weighted average values of the preexponential factor and the desorption energy, obtained from three experiments with heating rates from 0.6 to 3.2 °C/min, are: log10A(s−1)=12.2±0.5 and Ed=53.5±1.2 kcal/mol, where the uncertainties are 1σ sample standard deviations. The Arrhenius parameters of desorption of In from Ga-stabilized GaAs(100) are found to be similar to those of vaporization of pure In. This is consistent with the known tendency of In to form islands on GaAs surfaces, but could also reflect the similarity of the local environments of an In atom adsorbed on an In island and an In atom adsorbed on a Ga-terminated surface. The observed first-order kinetics and the constancy of the In(3d 5/2) XPS signal up to the temperature where desorption occurs indicates that if islands are formed they are small (〈10 A(ring) diameter) at the low coverage used here.
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    The Journal of Chemical Physics 91 (1989), S. 4360-4368 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Cooperative diffusion D of polyacrylamide gels in water was investigated by quasielastic light scattering both under the isotropically swollen state and under the uniaxially stretched and swollen state. The concentration (Ce) dependence of D for the isotropic gels having equilibrium degrees of swelling was measured by systematically changing crosslinking density of gels. The results yielded D=(3.4±0.5)×10−6 C0.76±0.03e cm2/s, in accord with a scaling prediction. For each of the gels prepared and having a given Ce, the uniaxial stretching was applied, and the values D were investigated as a function of extension ratio α and direction β with respect to the stretching direction. The results gave D (α,Ce)=(3.4±0.5)×10−6 αx Cye cm2/s, where x=2/3 for β=0° and −1/4 for β=90°, and y=0.76, independent of α and β. The results clearly indicate that upon increasing α, D increases and decreases, respectively, in the direction parallel and perpendicular to the stretching direction, implying suppression and enhancement of the concentration fluctuations as a result of the network being stiffened and softened in the respective directions.
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    The Journal of Chemical Physics 91 (1989), S. 4387-4400 
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    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The discrete chain representation of multiple scattering theory of the concentration dependence of the hydrodynamics of polymer solutions is applied to the calculation of the leading concentration correction to the dynamic structure factor S(k,t) and its first and second cumulants of individual labeled Gaussian chains in theta solutions at nonzero concentrations. Contributions are separated into those from overall translational and internal chain motions as well as couplings between different internal modes and between translation and internal modes, coupling that are introduced by interchain hydrodynamic interactions. The separate contributions are analyzed as a function of k and of t in order to isolate regions where certain contributions are dominant. As expected, short times and larger k tend to favor contributions from internal chain dynamics, while longer times and smaller k make concentration dependent translational effects predominate. Computations for shorter chains are extrapolated to provide the asymptotic long chain behavior.
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    The Journal of Chemical Physics 91 (1989), S. 4418-4419 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The interconversion tunneling frequencies for (HCl)2 and (DCl)2 are obtained from near-infrared absorption spectra of the H(D)Cl stretching transitions, to spectroscopic precision for the mixed 35Cl–37Cl dimers. A phenomenological model of the interconversion process explains several experimental observations, and provides good estimates of the splittings expected for the 35Cl–35Cl and 37Cl–37Cl species.
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    The Journal of Chemical Physics 91 (1989), S. 4425-4426 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The dissociation energy of boron hydride has been calculated ab initio using a very accurate theoretical model, with an expected accuracy of ±0.2 kcal mol−1. The values of 85.7 and 82.4 kcal mol−1 for De and D0, respectively, confirm the conclusion of Curtiss and Pople [J. Chem. Phys. 90, 2522 (1989)], that the predissociation limit of 82.6±0.4 kcal mol−1 might be close to the actual dissociation energy, and that an earlier proposed De of 78.9 kcal mol−1 is in error.
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    The Journal of Chemical Physics 91 (1989), S. 3525-3531 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The ultrafast photodynamics of four-coordinate nickel(II) porphyrins in noncoordinating solvents has been studied using femtosecond time resolved optical spectroscopy. Unambiguous evidence has been found for the formation of a metastable metal (d,d) excited state in less than 350 fs following excitation of the macrocycle. However, the transient absorption spectrum of this ligand-field electronic excited state continues to evolve and reaches the steady-state form only after about 20 ps. This spectral behavior and the attendant complex kinetics can be modeled phenomenologically in terms of a broad distribution of the (d,d) excited states evolving to a narrower distribution. The dynamics are associated with vibrational relaxation. Intramolecular and intermolecular contributions to this process are considered.
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    The Journal of Chemical Physics 91 (1989), S. 3571-3576 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: A new method for the calculation of bound state eigenvalues and eigenfunctions of the Schrödinger equation is presented. The Fourier grid Hamiltonian method is derived from the discrete Fourier transform algorithm. Its implementation and use is extremely simple, requiring the evaluation of the potential only at certain grid points and yielding directly the amplitude of the eigenfunctions at the same grid points.
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  • 70
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    Notes: The evaluation of free energy differences using the perturbation method or thermodynamic integration method requires special caution if multiple rotational isomeric states may exist in the system under investigation. In this article a recently suggested procedure to properly treat rotational isomeric states is illustrated with a molecular dynamics simulation of an aqueous solution of uncomplexed 18-crown-6 crown ether, as an example of a system in which large numbers of isomeric states may exist. By using very long molecular dynamics simulations, thermodynamic perturbation methods and symmetry arguments, the free energy of host organization into the conformation required to form the complex with K+ is estimated to be 2.6 kJ mol−1. It has also been found that the lowest energy conformations of 18-crown-6 in vacuo do not necessarily correspond to the most populated conformations in aqueous solution.
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  • 71
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    The Journal of Chemical Physics 91 (1989), S. 3689-3699 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Pulsed neutron diffraction measurements have been made on liquid 1,2-dichloroethane-d4 (DCE). The wide momentum-transfer range (∼0.3–50 A(ring)−1) available has been used to further refine previously measured molecular structure parameters as well as to test the validity of the inelasticity corrections applied. A measurement using chlorine isotopes on a steady (reactor) source served to partially separate the chlorine–chlorine and the chlorine–carbon plus chlorine–deuterium correlations. The isotopic difference curves were then analyzed and the relevant features of the distribution of internal dihedral angles [P(τ)] obtained by adequate inversion of the experimental difference–functions. The intermolecular pair correlation function was then derived and both sets of functions (from pulsed and steady sources) are compared and tentatively assigned.
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  • 72
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    The Journal of Chemical Physics 91 (1989), S. 3721-3723 
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    Notes: Brownian dynamics computer simulations are used to investigate the shape of the mean-squared end-to-end distance distribution function in the three regimes: (1) excluded volume; (2) θ; (3) collapsed. It is found that Mazur's function fits regime (1), that the Gaussian function fits regime (2), and that neither of these appear to describe the collapsed state. The implications of these results to theories of ring formation during polymerization is pointed out.
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  • 73
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    The Journal of Chemical Physics 91 (1989), S. 5154-5159 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Using a purely ab initio minimum energy path for the trans-tunneling motion in the HF dimer, the energy levels for the K-type rotation and trans-tunneling motion for (HF)2 and (DF)2 are calculated with a one-dimensional semirigid bender Hamiltonian and no adjustable parameters. The transition moments for rotation-tunneling transitions are calculated, using our ab initio value for the dipole moment of an isolated HF molecule, and we also calculate B¯ values. The energy levels we obtain are in close agreement with experiment; for example, the K=0 tunneling splitting in (HF)2 is calculated as 0.65 cm−1 compared to the experimental value of 0.658 69 cm−1. As well as showing that our ab initio minimum energy path is very good, the calculation demonstrates that the semirigid bender formalism is able to account quantitatively for the unusual K dependence of the rotational energies resulting from the quasilinear behavior, and that the trans-tunneling motion is separable from the other degrees of freedom. We use the results to predict the locations, and transition moments, of the ΔK=0 and ±1 subbands in the tunneling spectra of (HF)2 and (DF)2, many of which have not yet been observed.
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  • 74
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    The Journal of Chemical Physics 91 (1989), S. 5139-5153 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The problem of classical vs nonclassical structure of protonated acetylene (vinyl cation) C2H+3 has been studied using high resolution infrared spectroscopy. The spectrum has been observed in the 3.2 μm region in air-cooled and water-cooled plasmas using C2H2:H2:He mixtures and in liquid nitrogen-cooled plasmas using CH4:H2:He mixtures. The difference frequency spectrometer with the velocity modulation method has been used to conduct the Doppler-limited, high sensitivity spectroscopy.The observed vibration–rotation pattern with the band origin at 3142.2 cm−1 has been identified as due to the antisymmetric CH stretching ν6 band of the C2H+3 ion with the nonclassical (bridged) structure. The observed spectral pattern was anomalous, but definitive assignments could be made for a part of the spectrum using the ground state combination differences which fit to the usual asymmetric rotor pattern. The discrimination between the classical and nonclassical structures is based on the observed spectral intensity pattern due to spin statistical weights. Agreement of vibrational band patterns and the rotational constants with ab initio values gives supporting evidence. The anomaly of the spectrum is at least partly ascribed to the small energy difference between the classical and nonclassical structures and possible rearrangement between them, the idea used by organic chemists over the years in wet chemistry. Systematic splittings with the intensity ratio of 2:1 have been noticed in some parts of the spectrum indicating that the protons tunnel between the apex and the two end equilibrium positions of the bridged structure. Using a simplified internal rotation model proposed by Hougen, the barrier height of the tunneling has been estimated. Chemical kinetics in plasmas related to C2H+3 is also discussed.We conclude that (1) the nonclassical structure is lower in energy than the classical structure, and (2) the apex proton and the two end protons exchange their positions with a measurable time scale.
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  • 75
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    The Journal of Chemical Physics 91 (1989), S. 5164-5169 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The inelastic neutron scattering (INS) spectra of some ammonium halides and ammonium nitrate are analyzed in terms of the internal vibrations of the NH+4 ion convoluted with multiphonon lattice modes up to the eighth term. Due to the low mass of this ion, most of the intensity of the internal-mode region of the INS spectra is in the "phonon wings,'' differences between the salts in this spectral region being mainly due to differences in their lattice-mode spectra. Refinement of the lattice Debye–Waller factor is included in the profile refinement of interatomic force constants.
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  • 76
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    The Journal of Chemical Physics 91 (1989), S. 5160-5163 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: A new upper bound for the dissociation energy of acetylene, D00(HCC–H) =529.89(±0.01) kJ/mol, has been determined by Stark anticrossing spectroscopy. The zero-pressure extrapolated (unimolecular) decay rates of levels of S1 (A˜ 1Au) v'3=2 and 3 (quanta of the trans-bending vibration) increase upon application of an electric field of 113 kV/cm. We attribute this increase in molecular decay rate to predissociation rather than any other Stark-induced nonradiative or radiative phenomenon. The lowest level (v'3 =2, J'=2, K'=1) from which we have observed an increase in decay rate (i.e., predissociation) has an internal energy of 44 295.65 cm−1 relative to v=0, J=0 of S0 (X˜ 1∑+g). This corresponds to a value about 24 kJ/mol lower then the consensus upper bound result from four different recent experimental determinations (including one of ours) as well as current ab initio results. The new value agrees, however, with earlier work and with recent modeling studies of acetylene pyrolysis kinetics.
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  • 77
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    The Journal of Chemical Physics 91 (1989), S. 3792-3793 
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  • 78
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    The Journal of Chemical Physics 91 (1989), S. 2776-2778 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Electron paramagnetic resonance (EPR) studies performed at room tempertaure in Mn2+ doped Cs2NaYCl6 single crystals (elpasolite) showed that the Mn2+ ion occupies a tetragonal symmetry site in the cubic crystalline lattice. In contrast with previous results on elpasolite, where trivalent rare earth impurities occupy Oh sites, and divalent europium impurities occupy trigonal sites, this work reports, the first evidence of an impurity in a tetragonal symmetry site in this host with principal axes along 〈100〉 crystallographic directions. The unusually large total splitting of the EPR spectrum (∼10 000×10−4 cm−1) is discussed in order to establish a tentative model for the site.
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  • 79
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    The Journal of Chemical Physics 91 (1989), S. 3596-3602 
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    Notes: Novel rigorous upper and lower bounds, at primitive level, to general electron-repulsion integrals (ERIs) involving Gaussian basis sets have been derived and interconnections with the earlier works in the literature are brought out. New optimal strategies for a preemptive elimination of insignificant ERIs at atom and contraction levels are discussed and tested, resulting in a significant reduction in CPU time. Similar analysis is carried out for the computation of the molecular electrostatic potential for the first time in the literature, leading to a marked savings in computer time.
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  • 80
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    The Journal of Chemical Physics 91 (1989), S. 5185-5200 
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    Notes: Multiphoton ionization spectra have been obtained and analyzed for excitation in the 215–360 nm region from the X 3Σ−g, a 1Δg, and b 1Σ+g states of O2. The 0–0 band of the C 1Πg state is reported for the first time. Measurements of other vibrational bands terminating in the C 3Πg and d 1Πg states are in good agreement with determinations by other groups. Several vibrational levels (v'=0–5) of the 3dπg Rydberg complex have been assigned on the basis of (1) an analysis of the spin–orbit couplings between the (Λ,S) basis-set states, (2) spectral simulation, and (3) the behavior of the states when the excitation radiation is changed from linear to circular polarization.
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  • 81
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    The Journal of Chemical Physics 91 (1989), S. 5201-5207 
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    Notes: Diode laser transient absorption/gain spectroscopy is used to monitor time-dependent populations of high rotational levels in OD (v=0) produced in the reaction of O(1D)+D2. Pure rotational transitions on species with large dipole moments offer good sensitivity, full state resolution and μs time resolution in the present apparatus. Measured nascent populations of OD in the four highest rotational levels thermodynamically accessible in this reaction are in reasonable agreement with the reported results of earlier laser-induced-fluorescence measurements, in which corrections for transition moments and predissociation introduce increasing uncertainties at high rotational levels. The relaxation kinetics of the highest rotational levels are not hopelessly complex, and evidence is presented for strong, but not complete propensity for conservation of Λ doublet symmetry during rotational relaxation.
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  • 82
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    The Journal of Chemical Physics 91 (1989), S. 3647-3661 
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    Notes: A consistent simulation of ionic or strongly polar solutes in polar solvents presents a major challenge from both fundamental and practical aspects. The frequently used method of periodic boundary conditions (PBC) does not correctly take into account the symmetry of the solute field. Instead of using PBC, it is natural to model this type of system as a sphere (with the solute at the origin), but the boundary conditions to be used in such a model are not obvious. Early calculations performed with our surface constrained soft sphere dipoles (SCSSD) model indicated that the dipoles near the surface of the sphere will show unusual orientational preferences (they will overpolarize) unless a corrective force is included in the model, and thus we implemented polarization constraints in this spherical model of polar solutions. More recent approaches that treated the surface with stochastic dynamics, but did not take into account the surface polarization effects, were also found to exhibit these nonphysical orientational preferences. The present work develops a surface constrained all-atom solvent (SCAAS) model in order to consistently treat the surface polarization effects in all-atom molecular dynamics simulations. The SCAAS model, which was presented in a preliminary way in previous works, introduces surface constraints as boundary conditions in order to make the necessarily finite system behave as if it was part of an infinite system. The performance of the model with regard to various properties of bulk water is examined by comparing its results to those obtained by PBC simulations. The results obtained from SCAAS models of different sizes are found to be similar to each other and to the corresponding PBC results. The performance of the model in simulations of solvated ions is emphasized and a comparison of the results obtained with spheres of different sizes demonstrates that the model does not possess significant size dependence. This indicates that the model can be used with a relatively small number of solvent molecules for convergent simulation of structure, energetics, and dynamics of polar solutions. The much simpler fixedcenter Langevin dipoles (FCLD) model is also examined and found to provide a powerful tool for estimating solvation free energies. Finally, a preliminary study of the dielectric properties of the SCAAS model is reported and the potential of this model for exploring the correct implementation of the solvent reaction field is discussed.
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    The Journal of Chemical Physics 91 (1989), S. 3700-3706 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The first-order phase transition of the ferromagnetic Ising model driven by the magnetic field at temperatures below criticality is studied by Monte Carlo methods for a two-dimensional thin film geometry, L×M with two free boundaries of length M(very-much-greater-than)L, at which boundary fields act. This model study is relevant, in particular, for phase transitions in monolayers adsorbed at stepped surfaces. While in the bulk geometry (L→∞) this transition occurs for zero field in the present model, with the system "jumping'' from a state with uniformly positive magnetization to a state with uniformly negative magnetization, in the thin film geometry the transition occurs at a critical field H*∼L−1, and the two states between which the transition occurs are characterized by strongly nonuniform magnetization profiles across the film. These findings are in agreement with the scaling theory of Fisher and Nakanishi.
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  • 84
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    The Journal of Chemical Physics 91 (1989), S. 3724-3728 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: A simplified stability condition for the Hartree–Fock (HF) solution giving the self-consistent field crystal orbitals (SCF-CO) of the infinite one-dimensional system is derived. Since the present formulation, particularly for the systems having nearly or entirely degenerated highest occupied and the lowest unoccupied COs, contains only two physical parameters, that is, the density of states and the Coulomb repulsion integrals both at the Fermi level, it is tractable to examine the stability of the HF solutions of such polymers as well as the ordinary molecular systems. An example of its application to metallic trans-type polyacetylene is also shown.
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  • 85
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    The Journal of Chemical Physics 91 (1989), S. 3744-3761 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: An ensemble of distributed donor molecules that undergoes rotational transitions into a discrete excimer state has been analyzed, in an attempt to model distributed electronic relaxation and nonexponential fluorescence of aromatic polymers in presence of rotational sampling processes. In case of irreversible trapping, the donor survival function has been formulated in terms of the one-sided Laplace transform and specified for a modified Gaussian distribution to yield a closed-form expression for the donor decay. The formalism permits a time-dependent rate function to be derived that makes possible the construction of the excimer excitation function by means of the convolution theorem. In case of reversible constraints, a generalized treatment based upon time-dependent transition and transform matrices has been given which applies a perturbation technique for approximately solving the system of nonautonomous differential equations in the time domain. In the limit of weak coupling, the method develops approximate Mth order expressions (M=2,4,6, and 8) to the fluorescence response functions of donor and excimer. The perturbational solutions are well behaved up to relatively long time scales and they prove useful for providing the typical nonexponential time behavior of such a system affected by dispersion and dissociation. The physical restriction of this mathematical analysis (weak reversibility) has been addressed and the implications of distributed event times in future analyses of polymer fluorescence have been discussed.
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    The Journal of Chemical Physics 91 (1989), S. 2771-2775 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: 5,6-Dihydro-2H-thiopyran, CH2CH2CH=CHCH2S, has been synthesized and its far-infrared and Raman spectra recorded. Two series of sharp bands were observed originating from 139 and 235 cm−1 in the infrared spectrum for the out-of-plane ring-bending and the ring-twisting vibrations, respectively. A detailed energy level diagram including numerous excited states was determined for the two coupled vibrations. The two-dimensional potential energy surface, which satisfactorily fits more than two dozen observed transitions, was calculated to be V=2.431×104 x41 −0.383×104x21 +2.258×104x42 −1.966×104 x22 +1.026×105x21 x22 , where x1 is the ring-bending coordinate and x2 is the ring-twisting coordinate. The minimum energy on the potential surface corresponds to a twisting angle of 37.8° (the half-chair conformation). The lowest energy bent (boat) conformation corresponds to a saddle point 4130 cm−1 above the twisted conformation on the potential energy surface. The results are compared to analogous molecules and to molecular mechanics calculations.
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    The Journal of Chemical Physics 91 (1989), S. 2808-2813 
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    Notes: Photoabsorption cross sections of thiirane and thietane vapors have been studied in the 110–240 nm region using synchrotron radiation. A number of peaks from thiirane and thietane are arranged into four and five Rydberg series, respectively, converging to the first ionization potential. Many Rydberg peaks from both molecules are observed to possess vibronic structures. The vibrational progressions from thiirane are assigned to the CH2 wagging (ν4) and CS symmetry stretching (ν5) modes. For thietane, the CH2 wagging (ν5) and CS symmetry stretching (ν7) modes of the excited states are found to be active. Molecular geometries and vibrational frequencies for the excited states are discussed on the basis of ab initio calculations.
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    The Journal of Chemical Physics 91 (1989), S. 2840-2847 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Exact close-coupling calculations are used to evaluate the effectiveness of the coupled states approximation in the interpretation of low energy, noble gas methane collisions. The effect of the higher order angle dependent terms of the potential on the inelastic rotational transition was investigated. Calculations using only open channel basis functions were clearly different from converged calculations, but the differences were small enough to be negligible in comparison with experiment. It was shown that open channel coupled states calculations are of sufficient accuracy to evaluate the agreement of the potential model with experiment. The use of the coupled states approximation does not fully account for discrepancies between theory and experiment observed earlier.
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    The Journal of Chemical Physics 91 (1989), S. 2892-2897 
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    Notes: A modified general model for radiationless energy transfer is examined. The model does not rely on selection criteria and is intended to apply over the range of diffusion and resonance energy transfer parameters normally encountered in quenching experiments. Experimental data is compared with theoretical predictions and found to confirm the model's validity for a wide range of physical conditions.
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    The Journal of Chemical Physics 91 (1989), S. 2912-2921 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The photodissociation of aluminum clusters, Al+n (n=7–17), has been studied over a broad energy range (1.88–6.99 eV). Measurements of the lifetimes of the photoexcited clusters are described. Dissociation energies have been determined by comparing the measured lifetimes with the predictions of a simple RRKM model. The dissociation energies show an overall increase with cluster size, but there are substantial oscillations around n=7–8 and n=13–15. Cluster cohesive energies are derived from these results and from previous measurements of the dissociation energies of the smaller clusters. The cohesive energies of the larger clusters (n〉6) are in good agreement with the predictions of a simple model based on the bulk cohesive energy and the cluster surface energy. However, the cohesive energies are substantially larger than the results of recent ab initio calculations. The photodissociation spectrum of Al+8 has been measured and shows a broad absorption feature with a maximum ∼470 nm.
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  • 91
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    The Journal of Chemical Physics 91 (1989), S. 2102-2107 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The microwave spectrum of dichlorosilylene SiCl2 has been observed to characterize this molecule of chemical interest. The molecule was generated by the thermal reaction between silicon powder and tetrachlorosilane at about 1000 °C. The rotational constants and the centrifugal distortion constants were determined for the three isotopic species Si35Cl2, Si35Cl37Cl, and Si37Cl2. The nuclear quadrupole coupling constants were determined from triplet hyperfine splittings observed for several transitions. The asymmetry of the Cl nuclear quadrupole coupling tensor was found to be very large and was accounted for by π electron backdonation from Cl to Si.
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  • 92
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    The Journal of Chemical Physics 91 (1989), S. 2971-2979 
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    Notes: The structures and stabilities of N2 and its 15 possible first-row isoelectronic analogs (CO, BF, BeNe, NO+, CF+, BNe+, O2+2, NF2+, CNe2+, OF3+, NNe3+, ONe4+, F4+2, FNe5+, and Ne6+2) have been examined using ab initio molecular orbital theory. Equilibrium structures have been obtained at a variety of levels of theory including MP3/6-311G(d) and ST4CCD/6-311+G(2df ) and dissociation energies determined at the MP4/6-311+G(3d2f ) level. Full potential energy curves for dissociation, including dissociation barriers, have been obtained at the CASSCF/6-311G(d) level. Spectroscopic constants have also been determined at this level. For the neutral and monocation analogs of N2, the calculated equilibrium geometries, dissociation energies, and spectroscopic constants are in good agreement with the experimental values. The dication analogs of N2, namely O2+2, NF2+, and CNe2+, are all found to be kinetically stable species lying in deep potential wells. In particular, the hitherto unobserved NF2+ dication is predicted to have a short equilibrium bond length (1.102 A(ring)) and a large barrier (445 kJ mol−1) to dissociation to N++F+. Thus NF2+ should be experimentally accessible in the gas phase. The (experimentally known) O2+2 dication is predicted to contain the shortest bond between any two heavy atoms, our best estimate of the bond length being 1.052 A(ring). The first excited state (A 3Σ+u) of O2+2 is predicted to be unbound, and observed metastable decomposition processes are reinterpreted in terms of the ground-state (X 1Σ+g) potential surface. In agreement with previous theoretical studies, we find that CNe2+ is a kinetically stable species, albeit with a relatively long C–Ne bond length. The OF3+ trication is calculated to have a relatively short bond but lies in a well of depth only 23 kJ mol−1. The potential energy curves of the other highly charged species are found to be purely repulsive.
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    The Journal of Chemical Physics 91 (1989), S. 3002-3011 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The relative efficacy of using low order trucations with large reference space vs high order methods with small reference space is tested by comparing quasidegenerate many-body perturbation theory (QDMBPT) calculations of potential curves for the five lowest electronic states of LiH with the multireference coupled cluster calculations of Ben-Shlomo and Kaldor [J. Chem. Phys. 89, 956 (1988)]. The infinite order coupled cluster calculations use two configurational reference spaces involving the 2σ, 3σ, and 1π orbitals, while the QDMBPT computations are truncated at either second or third orders and employ the full active reference space formed either from the 2σ, 3σ, and 1π or from the 2σ, 3σ, 4σ, and 1π orbitals. This gives us the opportunity of testing the dependence of QDMBPT computations on the size of reference space, the available freedom in choosing valence orbitals and orbital energies, and the order of truncation. Second order, four valence orbital space QDMBPT calculations provide good agreement with the repulsive portion of the coupled cluster potentials, but yield a separated atom limit that is too high and that therefore distorts the remainder of the potential. Third order improves the separated atom limit considerably, providing good agreement with the coupled cluster calculations. The "full chemical'' five orbital reference space, on the other hand, yields very good agreement with coupled cluster potentials when using only the simpler second order QDMBPT calculations, and third order corrections in this case are very small but generally improve agreement with coupled cluster potentials. The five orbital reference space calculations are quite insensitive to a wide range of different choices of valence orbitals and orbital energies, demonstrating a robustness to the QDMBPT formalism used.
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    The Journal of Chemical Physics 91 (1989), S. 3045-3055 
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    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The hypernetted-chain (HNC) approximation is solved for fluids of dipolar hard ellipsoids and the structural, thermodynamic, and dielectric properties of the isotropic phase are discussed in some detail. Both prolate and oblate particles are considered and the isotropic–nematic transition is investigated using density functional theory (DFT). For fluids of prolate particles dipolar forces are found to have a significant effect upon the isotropic–nematic transition which occurs at lower densities as the dipole moment is increased. For the oblate case the dipolar interactions have only a very small, if any, influence upon the isotropic–nematic transition density. For both prolate and oblate particles the present HNC/DFT calculations do not predict ferroelectric nematic phases.
    Type of Medium: Electronic Resource
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  • 95
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5313-5315 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The ν3 (O–Si stretch) fundamental bands of the HOSi+ and DOSi+ molecular ions in the 9 μm region have been detected for the first time, using a tunable infrared diode laser spectrometer and a hollow cathode discharge cell. Analysis of the results yielded accurate values for the molecular rotational and centrifugal distortion parameters, as well as for the band origins, which are 1127.009 cm−1 for HOSi+ and 1103.112 cm−1 for DOSi+ . The ground vibrational state parameters are in excellent agreement with those determined from the ν1 bands of the two isotopes.
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  • 96
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5324-5328 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Fragment ions from N2 in the states of (K)−1(nl)1 have been measured at 54.7° with respect to the polarization direction of the incident photon by using a time-of-flight (TOF) mass spectrometer. Simulation fitting calculation to the measured TOF spectra gave distributions of the kinetic energy for these ions. Ion yield spectra observed showed that no singly charged molecular ion was produced from the states of (K)−1(nl)1 in contrast to that of (K)−1(1πg)1. These results are discussed in connection to the dissociation pathway of N2 in these states.
    Type of Medium: Electronic Resource
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  • 97
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5329-5334 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Dissociation of O2 stimulated by soft x-ray absorption has been studied by using a monochromatized synchrotron radiation and a time-of-flight mass spectrometer. The parent molecular ion O+2 was formed only at 531 eV (excitation of 1s→1πg), and a fragment ion O+ had the highest intensity in all the energies giving core–hole states. The measured time-of-flight spectra were reproduced by a simulation calculation, which provided kinetic energy distributions of O+ and O++. The dissociation pathways from the core–hole states of O2 were discussed using the obtained kinetic energy distribution and ion intensity ratios as well as Auger electron spectra in the literature.
    Type of Medium: Electronic Resource
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  • 98
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5316-5323 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The general theory for inelastic scattering of molecules 1Δ electronic states is outlined and applied to the specific case of 1Δ states arising from a π2 electron occupancy, e.g., NH(a 1Δ). Integral cross sections for rotational transitions out of the lowest rotational level (J=2) of NH(a 1Δ) v=0 are reported for several targets. A pulsed beam of rotationally cold NH(a 1Δ) was produced by 193 nm photolysis of a dilute mixture of hydrazoic acid in nitrogen seed gas at the tip of a nozzle. The target beam was also prepared as a pulsed supersonic beam. The final rotational state distribution was measured in the collision zone by laser fluorescence excitation. The state-to-state cross sections were found to decrease significantly with increasing final rotational quantum number J'. The magnitude of the J=2→J'=3 cross sections were compared for the different targets. Isotopic scrambling in NH(a 1Δ)–D2 collisions was also searched for but not observed.
    Type of Medium: Electronic Resource
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  • 99
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5335-5342 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The yield of metastable oxygen atoms through dissociative recombination of O+2 ions with electrons has been studied using a plasma flow tube experiment. For O+2 with high vibrational excitation (around v=9) it was found that half of the oxygen atoms are formed on the O(1D) state and that the branching ratio toward O(1S) is large (∼0.4). Using Xe+ instead of Ar+ as precursor ions, it was shown that the O(1S) yield is much less for ions with low vibrational excitation. However, the present experimental results are not compatible with the extremely low theoretical value of this yield which was reported recently for O+2 (v=0).
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  • 100
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5343-5351 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Quenching and vibrational energy transfer in the B2Π state of the NS free radical have been studied using temporally and spectrally resolved laser-induced fluorescence in a low-pressure discharge flow reactor. The collision partners were He, Ar, H2, N2, O2, SF6, CO2, and N2O. Total removal cross sections show an oscillatory behavior with v' in the range of unperturbed levels, v'=4–7, for all colliders studied save O2 where a nearly monotonic increase is seen. Vibrational transfer occurs for H2 and the polyatomics; the rates vary little with v'. Δv=2 transfer occurs with the polyatomic colliders for v'=5. Fluorescence decay traces from the perturbed v'=3 and 8 levels differ from the unperturbed levels and from each other. v'=3 is perturbed by quartets and shows "gateway'' level behavior whereas v'=8 is perturbed by a doublet and shows efficient interelectronic transfer for all rotational levels.
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