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  • 1
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    American Meteorological Society
    In:  EPIC3Journal of Climate, American Meteorological Society, 35(23), pp. 7811-7831, ISSN: 0894-8755
    Publikationsdatum: 2023-06-23
    Beschreibung: Numerical simulations allow us to gain a comprehensive understanding of the underlying mechanisms of past, present, and future climate changes. The mid-Holocene (MH) and the last interglacial (LIG) were the two most recent warm episodes of Earth’s climate history and are the focus of paleoclimate research. Here, we present results of MH and LIG simulations with two versions of the state-of-the-art Earth system model AWI-ESM. Most of the climate changes in MH and LIG compared to the preindustrial era are agreed upon by the two model versions, including 1) enhanced seasonality in surface temperature that is driven by the redistribution of seasonal insolation; 2) a northward shift of the intertropical convergence zone (ITCZ) and tropical rain belt; 3) a reduction in annual mean Arctic sea ice concentration; 4) weakening and northward displacement of the Northern Hemisphere Hadley circulation, which is related to the decrease and poleward shift of the temperature gradient from the subtropical to the equator in the Northern Hemisphere; 5) a westward shift of the Indo-Pacific Walker circulation due to anomalous warming over the Eurasia and North Africa during boreal summer; and 6) an expansion and intensification of Northern Hemisphere summer monsoon rainfall, with the latter being dominated by the dynamic component of moisture budget (i.e., the strengthening of wind circulation). However, the simulated responses of the Atlantic meridional overturning circulation (AMOC) in the two models yield different results for both the LIG and the MH. AMOC anomalies between the warm interglacial and preindustrial periods are associated with changes in North Atlantic westerly winds and stratification of the water column at the North Atlantic due to changes in ocean temperature, salinity, and density.
    Repository-Name: EPIC Alfred Wegener Institut
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  • 2
    Publikationsdatum: 2023-02-25
    Beschreibung: Author Posting. © American Meteorological Society, 2022. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 52(11), (2022): 2841–2852, https://doi.org/10.1175/jpo-d-22-0025.1.
    Beschreibung: Prediction of rapid intensification in tropical cyclones prior to landfall is a major societal issue. While air–sea interactions are clearly linked to storm intensity, the connections between the underlying thermal conditions over continental shelves and rapid intensification are limited. Here, an exceptional set of in situ and satellite data are used to identify spatial heterogeneity in sea surface temperatures across the inner core of Hurricane Sally (2020), a storm that rapidly intensified over the shelf. A leftward shift in the region of maximum cooling was observed as the hurricane transited from the open gulf to the shelf. This shift was generated, in part, by the surface heat flux in conjunction with the along- and across-shelf transport of heat from storm-generated coastal circulation. The spatial differences in the sea surface temperatures were large enough to potentially influence rapid intensification processes suggesting that coastal thermal features need to be accounted for to improve storm forecasting as well as to better understand how climate change will modify interactions between tropical cyclones and the coastal ocean.
    Beschreibung: This research was made possible by the NOAA RESTORE Science Program (NA17NOS4510101 and NA19NOS4510194) and the NASA Physical Oceanography program (80NSSC21K0553 and WBS 281945.02.25.04.67) and NOAA IOOS program via GCOOS (NA16NOS0120018). The authors declare that they have no competing interests.
    Schlagwort(e): Seas/gulfs/bays ; Atmosphere–ocean interaction ; Currents ; Tropical cyclones ; Buoy observations ; In situ oceanic observations
    Repository-Name: Woods Hole Open Access Server
    Materialart: Article
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  • 3
    Publikationsdatum: 2023-02-25
    Beschreibung: Author Posting. © American Meteorological Society, 2022. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 52(8), (2022): 1797–1815, https://doi.org/10.1175/JPO-D-21-0288.1.
    Beschreibung: Intruding slope water is a major source of nutrients to sustain the high biological productivity in the Gulf of Maine (GoM). Slope water intrusion into the GoM is affected by Gulf Stream warm-core rings (WCRs) impinging onto the nearby shelf edge. This study combines long-term mooring measurements, satellite remote sensing data, an idealized numerical ocean model, and a linear coastal-trapped wave (CTW) model to examine the impact of WCRs on slope water intrusion into the GoM through the Northeast Channel. Analysis of satellite sea surface height and temperature data shows that the slope sea region off the GoM is a hotspot of ring activities. A significant linear relationship is found between interannual variations of ring activities in the slope sea region off the GoM and bottom salinity at the Northeast Channel, suggesting the importance of WCRs in modulating variability of intruding slope water. Analysis of the mooring data reveals enhanced slope water intrusion through bottom-intensified along-channel flow following impingements of WCRs on the nearby shelf edge. Numerical simulations qualitatively reproduce the observed WCR impingement processes and associated episodic enhancement of slope water intrusion in the Northeast Channel. Diagnosis of the model result indicates that baroclinic CTWs excited by the ring–topography interaction are responsible for the episodically intensified subsurface along-channel inflow, which carries more slope water into the GoM. A WCR that impinges onto the shelf edge to the northeast of the Northeast Channel tends to generate stronger CTWs and cause stronger enhancement of the slope water intrusion into the GoM.
    Beschreibung: This study is supported by the National Science Foundation through Grant OCE-1634965.
    Schlagwort(e): Continental shelf/slope ; Channel flows ; Mesoscale processes ; In situ oceanic observations ; Satellite observations ; Numerical analysis/modeling
    Repository-Name: Woods Hole Open Access Server
    Materialart: Article
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  • 4
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    American Meteorological Society
    In:  EPIC3Journal of Climate, American Meteorological Society, pp. 1-40, ISSN: 0894-8755
    Publikationsdatum: 2023-09-04
    Beschreibung: 〈jats:title〉Abstract〈/jats:title〉 〈jats:p〉Tipping points in the Earth system describe critical thresholds beyond which a single component, part of the system, or the system as a whole changes from one stable state to another. In the present-day Southern Ocean, the Weddell Sea constitutes an important dense-water formation site, associated with efficient deep-ocean carbon and oxygen transfer and low ice-shelf basal melt rates. Here, a regime shift will occur when continental shelves are continuously flushed with warm, oxygen-poor offshore waters from intermediate depth, leading to less efficient deep-ocean carbon and oxygen transfer and higher ice-shelf basal melt rates. We use a global ocean–biogeochemistry model including ice-shelf cavities and an eddy-permitting grid in the southern Weddell Sea to address the susceptibility of this region to such a system change for four 21〈jats:sup〉st〈/jats:sup〉-century emission scenarios. Assessing the projected changes in shelf–open ocean density gradients, bottom-water properties, and on-shelf heat transport, our results indicate that the Weddell Sea undergoes a regime shift by 2100 in the highest-emission scenario SSP5-8.5, but not yet in the lower-emission scenarios. The regime shift is imminent by 2100 in the scenarios SSP3-7.0 and SSP2-4.5, but avoidable under the lowest-emission scenario SSP1-2.6. While shelf-bottom waters freshen and acidify everywhere, bottom waters in the Filchner Trough undergo accelerated warming and deoxygenation following the system change, with implications for local ecosystems and ice-shelf basal melt. Additionally, deep-ocean carbon and oxygen transfer decline, implying that the local changes ultimately affect ocean circulation, climate, and ecosystems globally.〈/jats:p〉
    Repository-Name: EPIC Alfred Wegener Institut
    Materialart: Article , isiRev
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  • 5
    Publikationsdatum: 2023-08-29
    Beschreibung: This study focuses on the changes in diet and mobility of people buried in the La Sassa cave (Latium, Central Italy) during the Copper and Bronze Ages to contribute to the understanding of the complex contemporary population dynamics in Central Italy. To that purpose, carbon and nitrogen stable isotope analyses, strontium isotope analyses, and FT-IR evaluations were performed on human and faunal remains from this cave. The stable isotope analyses evidence a slight shift in diet between Copper and Bronze Age individuals, which becomes prominent in an individual, dating from a late phase, when the cave was mainly used as a cultic shelter. This diachronic study documents an increased dietary variability due to the introduction of novel resources in these protohistoric societies, possibly related to the southward spread of northern human groups into Central Italy. This contact between different cultures is also testified by the pottery typology found in the cave. The latter shows an increase in cultural intermingling starting during the beginning of the middle Bronze Age. The local mobility during this phase likely involved multiple communities scattered throughout an area of a few kilometers around the cave, which used the latter as a burial site both in the Copper and Bronze ages.
    Beschreibung: Published
    Beschreibung: e0288637
    Beschreibung: 6A. Geochimica per l'ambiente e geologia medica
    Beschreibung: 6SR VULCANI – Servizi e ricerca per la società
    Beschreibung: 7SR AMBIENTE – Servizi e ricerca per la società
    Beschreibung: JCR Journal
    Schlagwort(e): La Sassa cave (Central Italy) ; population dynamics ; nitrogen isotope ; strontium isotope
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 6
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    American Meteorological Society
    In:  EPIC3Bulletin of the American Meteorological Society, American Meteorological Society, 104(1), pp. e208-e242, ISSN: 0003-0007
    Publikationsdatum: 2023-04-26
    Beschreibung: Mechanisms behind the phenomenon of Arctic amplification are widely discussed. To contribute to this debate, the (AC)3 project was established in 2016 (www.ac3-tr.de/). It comprises modeling and data analysis efforts as well as observational elements. The project has assembled a wealth of ground-based, airborne, shipborne, and satellite data of physical, chemical, and meteorological properties of the Arctic atmosphere, cryosphere, and upper ocean that are available for the Arctic climate research community. Short-term changes and indications of long-term trends in Arctic climate parameters have been detected using existing and new data. For example, a distinct atmospheric moistening, an increase of regional storm activities, an amplified winter warming in the Svalbard and North Pole regions, and a decrease of sea ice thickness in the Fram Strait and of snow depth on sea ice have been identified. A positive trend of tropospheric bromine monoxide (BrO) column densities during polar spring was verified. Local marine/biogenic sources for cloud condensation nuclei and ice nucleating particles were found. Atmospheric–ocean and radiative transfer models were advanced by applying new parameterizations of surface albedo, cloud droplet activation, convective plumes and related processes over leads, and turbulent transfer coefficients for stable surface layers. Four modes of the surface radiative energy budget were explored and reproduced by simulations. To advance the future synthesis of the results, cross-cutting activities are being developed aiming to answer key questions in four focus areas: lapse rate feedback, surface processes, Arctic mixed-phase clouds, and airmass transport and transformation.
    Repository-Name: EPIC Alfred Wegener Institut
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  • 7
    Publikationsdatum: 2023-01-27
    Beschreibung: Author Posting. © American Meteorological Society, 2022. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 52(8), (2022): 1705-1730, https://doi.org/10.1175/jpo-d-21-0243.1.
    Beschreibung: Formation and evolution of barrier layers (BLs) and associated temperature inversions (TIs) were investigated using a 1-yr time series of oceanic and air–sea surface observations from three moorings deployed in the eastern Pacific fresh pool. BL thickness and TI amplitude showed a seasonality with maxima in boreal summer and autumn when BLs were persistently present. Mixed layer salinity (MLS) and mixed layer temperature (MLT) budgets were constructed to investigate the formation mechanism of BLs and TIs. The MLS budget showed that BLs were initially formed in response to horizontal advection of freshwater in boreal summer and then primarily maintained by precipitation. The MLT budget revealed that penetration of shortwave radiation through the mixed layer base is the dominant contributor to TI formation through subsurface warming. Geostrophic advection is a secondary contributor to TI formation through surface cooling. When the BL exists, the cooling effect from entrainment and the warming effect from detrainment are both significantly reduced. In addition, when the BL is associated with the presence of a TI, entrainment works to warm the mixed layer. The presence of BLs makes the shallower mixed layer more sensitive to surface heat and freshwater fluxes, acting to enhance the formation of TIs that increase the subsurface warming via shortwave penetration.
    Beschreibung: SK is supported by JSPS Overseas Research Fellowships. JS and SK are supported by NASA Grant 80NSSC18K1500. JTF and the mooring deployment were funded by NASA Grants NNX15AG20G and 80NSSC18K1494. DZ is supported by NASA Grant 80NSSC18K1499. This publication is partially funded by the Cooperative Institute for Climate, Ocean, and Ecosystem Studies (CICOES) under NOAA Cooperative Agreement NA20OAR4320271, Contribution 2021-1152. This is PMEL Contribution 5268.
    Beschreibung: 2023-01-27
    Schlagwort(e): Ocean ; North Pacific Ocean ; Tropics ; Entrainment ; Oceanic mixed layer ; Salinity
    Repository-Name: Woods Hole Open Access Server
    Materialart: Article
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  • 8
    Publikationsdatum: 2023-02-01
    Beschreibung: Author Posting. © American Meteorological Society, 2022. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 52(8), (2022): 1927-1943, https://doi.org/10.1175/jpo-d-21-0124.1.
    Beschreibung: The Galápagos Archipelago lies on the equator in the path of the eastward flowing Pacific Equatorial Undercurrent (EUC). When the EUC reaches the archipelago, it upwells and bifurcates into a north and south branch around the archipelago at a latitude determined by topography. Since the Coriolis parameter (f) equals zero at the equator, strong velocity gradients associated with the EUC can result in Ertel potential vorticity (Q) having sign opposite that of planetary vorticity near the equator. Observations collected by underwater gliders deployed just west of the Galápagos Archipelago during 2013–16 are used to estimate Q and to diagnose associated instabilities that may impact the Galápagos Cold Pool. Estimates of Q are qualitatively conserved along streamlines, consistent with the 2.5-layer, inertial model of the EUC by Pedlosky. The Q with sign opposite of f is advected south of the Galápagos Archipelago when the EUC core is located south of the bifurcation latitude. The horizontal gradient of Q suggests that the region between 2°S and 2°N above 100 m is barotropically unstable, while limited regions are baroclinically unstable. Conditions conducive to symmetric instability are observed between the EUC core and the equator and within the southern branch of the undercurrent. Using 2-month and 3-yr averages, e-folding time scales are 2–11 days, suggesting that symmetric instability can persist on those time scales.
    Beschreibung: This work was supported by the National Science Foundation (Grants OCE-1232971 and OCE-1233282), the NASA Earth and Space Science Fellowship Program (Grant 80NSSC17K0443), and the Global Ocean Monitoring and Observing Program of the National Oceanographic and Atmospheric Administration (NA13OAR4830216). Color maps are from Thyng et al. (2016).
    Beschreibung: 2023-02-01
    Schlagwort(e): Currents ; In situ oceanic observations ; Instability ; Mixing ; Ocean dynamics ; Pacific Ocean ; Potential vorticity ; Tropics
    Repository-Name: Woods Hole Open Access Server
    Materialart: Article
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  • 9
    Publikationsdatum: 2023-02-01
    Beschreibung: Author Posting. © American Meteorological Society, 2022. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of the Atmospheric and Oceanic Technology 39(8), (2022): 1183-1198, https://doi.org/10.1175/jtech-d-21-0068.1.
    Beschreibung: Horizontal kinematic properties, such as vorticity, divergence, and lateral strain rate, are estimated from drifter clusters using three approaches. At submesoscale horizontal length scales O(1–10)km, kinematic properties become as large as planetary vorticity f, but challenging to observe because they evolve on short time scales O(hourstodays). By simulating surface drifters in a model flow field, we quantify the sources of uncertainty in the kinematic property calculations due to the deformation of cluster shape. Uncertainties arise primarily due to (i) violation of the linear estimation methods and (ii) aliasing of unresolved scales. Systematic uncertainties (iii) due to GPS errors, are secondary but can become as large as (i) and (ii) when aspect ratios are small. Ideal cluster parameters (number of drifters, length scale, and aspect ratio) are determined and error functions estimated empirically and theoretically. The most robust method—a two-dimensional, linear least squares fit—is applied to the first few days of a drifter dataset from the Bay of Bengal. Application of the length scale and aspect-ratio criteria minimizes errors (i) and (ii), and reduces the total number of clusters and so computational cost. The drifter-estimated kinematic properties map out a cyclonic mesoscale eddy with a surface, submesoscale fronts at its perimeter. Our analyses suggest methodological guidance for computing the two-dimensional kinematic properties in submesoscale flows, given the recently increasing quantity and quality of drifter observations, while also highlighting challenges and limitations.
    Beschreibung: This research was supported by the Office of Naval Research (ONR) Departmental Research Initiative ASIRI under Grant N00014-13-1-0451 (SE and AM) and Grant N00014-13-1-0477 (VH and LC). The authors thank the captain and crew of the R/V Roger Revelle, and Andrew Lucas with the Multiscale Ocean Dynamics group at the Scripps Institution for Oceanography for providing the FastCTD data collected in 2015, which was supported by ONR Grant N00014-13-1-0489, as well as Eric D’Asaro for helpful discussions and Lance Braasch for assistance with the drifter dataset. AM and SE further thank NSF (Grant OCE-I434788) and ONR (Grant N00014-16-1-2470) for support. VH and LC were additionally supported by ONR Grants N00014-15-1-2286, N00014-14-1-0183, N00014-19-1-26-91 and NOAA Global Drifter Program (GDP) Grant NA15OAR4320071.
    Beschreibung: 2023-02-01
    Schlagwort(e): Indian Ocean ; Eddies ; Frontogenesis/frontolysis ; Fronts ; Lagrangian circulation/transport ; Ocean circulation ; Ocean dynamics
    Repository-Name: Woods Hole Open Access Server
    Materialart: Article
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  • 10
    Publikationsdatum: 2023-02-01
    Beschreibung: Author Posting. © American Meteorological Society, 2022. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Climate 35(17), (2022): 5465-5482, https://doi.org/10.1175/jcli-d-21-0671.1.
    Beschreibung: Understanding the contribution of ocean circulation to glacial–interglacial climate change is a major focus of paleoceanography. Specifically, many have tried to determine whether the volumes and depths of Antarctic- and North Atlantic–sourced waters in the deep ocean changed at the Last Glacial Maximum (LGM; ∼22–18 kyr BP) when atmospheric pCO2 concentrations were 100 ppm lower than the preindustrial. Measurements of sedimentary geochemical proxies are the primary way that these deep ocean structural changes have been reconstructed. However, the main proxies used to reconstruct LGM Atlantic water mass geometry provide conflicting results as to whether North Atlantic–sourced waters shoaled during the LGM. Despite this, a number of idealized modeling studies have been advanced to describe the physical processes resulting in shoaled North Atlantic waters. This paper aims to critically assess the approaches used to determine LGM Atlantic circulation geometry and lay out best practices for future work. We first compile existing proxy data and paleoclimate model output to deduce the processes responsible for setting the ocean distributions of geochemical proxies in the LGM Atlantic Ocean. We highlight how small-scale mixing processes in the ocean interior can decouple tracer distributions from the large-scale circulation, complicating the straightforward interpretation of geochemical tracers as proxies for water mass structure. Finally, we outline promising paths toward ascertaining the LGM circulation structure more clearly and deeply.
    Beschreibung: S.K.H. was supported by the Investment in Science Fund at WHOI and the John E. and Anne W. Sawyer Endowed Fund in Support of Scientific Staff. F.J.P. was supported by a Stanback Postdoctoral Fellowship at Caltech.
    Beschreibung: 2023-02-01
    Schlagwort(e): Diapycnal mixing ; Meridional overturning circulation ; Ocean circulation
    Repository-Name: Woods Hole Open Access Server
    Materialart: Article
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  • 11
    Publikationsdatum: 2023-02-17
    Beschreibung: Author Posting. © American Meteorological Society, 2022. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of the Atmospheric and Oceanic Technology 39(10), (2022): 1525–1539, https://doi.org/10.1175/jtech-d-21-0186.1.
    Beschreibung: The static and dynamic performances of the RBRargo3 are investigated using a combination of laboratory-based and in situ datasets from floats deployed as part of an Argo pilot program. Temperature and pressure measurements compare well to co-located reference data acquired from shipboard CTDs. Static accuracy of salinity measurements is significantly improved using 1) a time lag for temperature, 2) a quadratic pressure dependence, and 3) a unit-based calibration for each RBRargo3 over its full pressure range. Long-term deployments show no significant drift in the RBRargo3 accuracy. The dynamic response of the RBRargo3 demonstrates the presence of two different adjustment time scales: a long-term adjustment O(120) s, driven by the temperature difference between the interior of the conductivity cell and the water, and a short-term adjustment O(5–10) s, associated to the initial exchange of heat between the water and the inner ceramic. Corrections for these effects, including dependence on profiling speed, are developed.
    Schlagwort(e): Data processing/distribution ; In situ oceanic observations ; Profilers ; Oceanic
    Repository-Name: Woods Hole Open Access Server
    Materialart: Article
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  • 12
    Publikationsdatum: 2023-02-28
    Beschreibung: Author Posting. © American Meteorological Society, 2022. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 52(12),(2022): 3199-3219, https://doi.org/10.1175/jpo-d-22-0009.1.
    Beschreibung: The abyssal overturning circulation is thought to be primarily driven by small-scale turbulent mixing. Diagnosed water-mass transformations are dominated by rough topography “hotspots,” where the bottom enhancement of mixing causes the diffusive buoyancy flux to diverge, driving widespread downwelling in the interior—only to be overwhelmed by an even stronger upwelling in a thin bottom boundary layer (BBL). These water-mass transformations are significantly underestimated by one-dimensional (1D) sloping boundary layer solutions, suggesting the importance of three-dimensional physics. Here, we use a hierarchy of models to generalize this 1D boundary layer approach to three-dimensional eddying flows over realistically rough topography. When applied to the Mid-Atlantic Ridge in the Brazil Basin, the idealized simulation results are roughly consistent with available observations. Integral buoyancy budgets isolate the physical processes that contribute to realistically strong BBL upwelling. The downward diffusion of buoyancy is primarily balanced by upwelling along the sloping canyon sidewalls and the surrounding abyssal hills. These flows are strengthened by the restratifying effects of submesoscale baroclinic eddies and by the blocking of along-ridge thermal wind within the canyon. Major topographic sills block along-thalweg flows from restratifying the canyon trough, resulting in the continual erosion of the trough’s stratification. We propose simple modifications to the 1D boundary layer model that approximate each of these three-dimensional effects. These results provide local dynamical insights into mixing-driven abyssal overturning, but a complete theory will also require the nonlocal coupling to the basin-scale circulation.
    Beschreibung: We acknowledge funding support from National Science Foundation Awards 1536515, 1736109, and 2149080. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship Program under Grant 174530.
    Beschreibung: 2023-05-18
    Schlagwort(e): Abyssal circulation ; Diapycnal mixing ; Meridional overturning circulation ; Topographic effects ; Upwelling/downwelling ; Bottom currents/bottom water
    Repository-Name: Woods Hole Open Access Server
    Materialart: Article
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  • 13
    Publikationsdatum: 2023-02-28
    Beschreibung: Author Posting. © American Meteorological Society, 2022. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 52(6), (2022): 1091–1110, https://doi.org/10.1175/JPO-D-21-0068.1.
    Beschreibung: Hundreds of full-depth temperature and salinity profiles collected by Deepglider autonomous underwater vehicles (AUVs) in the North Atlantic reveal robust signals in eddy isopycnal vertical displacement and horizontal current throughout the entire water column. In separate glider missions southeast of Bermuda, subsurface-intensified cold, fresh coherent vortices were observed with velocities exceeding 20 cm s−1 at depths greater than 1000 m. With vertical resolution on the order of 20 m or less, these full-depth glider slant profiles newly permit estimation of scaled vertical wavenumber spectra from the barotropic through the 40th baroclinic mode. Geostrophic turbulence theory predictions of spectral slopes associated with the forward enstrophy cascade and proportional to inverse wavenumber cubed generally agree with glider-derived quasi-universal spectra of potential and kinetic energy found at a variety of locations distinguished by a wide range of mean surface eddy kinetic energy. Water-column average spectral estimates merge at high vertical mode number to established descriptions of internal wave spectra. Among glider mission sites, geographic and seasonal variability implicate bottom drag as a mechanism for dissipation, but also the need for more persistent sampling of the deep ocean.
    Beschreibung: This work was funded by NSF Grant 1736217 and would not have been possible without the help of Kirk O’Donnell, James Bennett, Noel Pelland, and all contributors to Deepglider development. We additionally thank the captain crew of the R/V Atlantic Explorer and the BATS team at the Bermuda Institute of Ocean Sciences, particularly Rod Johnson, as well as Seakeepers International for their professionalism, capability, and generous assistance in deploying and recovering gliders.
    Schlagwort(e): North Atlantic Ocean ; Eddies ; Mesoscale processes ; Turbulence ; Energy transport ; In situ oceanic observations ; Oceanic variability
    Repository-Name: Woods Hole Open Access Server
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  • 14
    Publikationsdatum: 2023-03-02
    Beschreibung: Author Posting. © American Meteorological Society, 2022. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 52(12), (2022): 3221–3240, https://doi.org/10.1175/jpo-d-22-0010.1.
    Beschreibung: Small-scale mixing drives the diabatic upwelling that closes the abyssal ocean overturning circulation. Indirect microstructure measurements of in situ turbulence suggest that mixing is bottom enhanced over rough topography, implying downwelling in the interior and stronger upwelling in a sloping bottom boundary layer. Tracer release experiments (TREs), in which inert tracers are purposefully released and their dispersion is surveyed over time, have been used to independently infer turbulent diffusivities—but typically provide estimates in excess of microstructure ones. In an attempt to reconcile these differences, Ruan and Ferrari derived exact tracer-weighted buoyancy moment diagnostics, which we here apply to quasi-realistic simulations. A tracer’s diapycnal displacement rate is exactly twice the tracer-averaged buoyancy velocity, itself a convolution of an asymmetric upwelling/downwelling dipole. The tracer’s diapycnal spreading rate, however, involves both the expected positive contribution from the tracer-averaged in situ diffusion as well as an additional nonlinear diapycnal distortion term, which is caused by correlations between buoyancy and the buoyancy velocity, and can be of either sign. Distortion is generally positive (stretching) due to bottom-enhanced mixing in the stratified interior but negative (contraction) near the bottom. Our simulations suggest that these two effects coincidentally cancel for the Brazil Basin Tracer Release Experiment, resulting in negligible net distortion. By contrast, near-bottom tracers experience leading-order distortion that varies in time. Errors in tracer moments due to realistically sparse sampling are generally small (〈20%), especially compared to the O(1) structural errors due to the omission of distortion effects in inverse models. These results suggest that TREs, although indispensable, should not be treated as “unambiguous” constraints on diapycnal mixing.
    Beschreibung: We acknowledge funding support from National Science Foundation Awards 1536515 and 1736109. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship Program under Grant 174530. This research is also supported by the NOAA Climate and Global Change Postdoctoral Fellowship Program, administered by UCAR’s Cooperative Programs for the Advancement of Earth System Science (CPAESS) under Award NA18NWS4620043B.
    Beschreibung: 2023-05-18
    Schlagwort(e): Diapycnal mixing ; Diffusion ; Upwelling/downwelling ; Bottom currents/bottom water ; Tracers
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  • 15
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    Unbekannt
    American Meteorological Society
    In:  EPIC3Journal of Physical Oceanography, American Meteorological Society, 54(4), pp. 1003-1018, ISSN: 0022-3670
    Publikationsdatum: 2024-04-25
    Beschreibung: Coastal upwelling, driven by alongshore winds and characterized by cold sea surface temperatures and high upper-ocean nutrient content, is an important physical process sustaining some of the oceans’ most productive ecosystems. To fully understand the ocean properties in eastern boundary upwelling systems, it is important to consider the depth of the source waters being upwelled, as it affects both the SST and the transport of nutrients toward the surface. Here, we construct an upwelling source depth distribution for parcels at the surface in the upwelling zone. We do so using passive tracers forced at the domain boundary for every model depth level to quantify their contributions to the upwelled waters. We test the dependence of this distribution on the strength of the wind stress and stratification using high-resolution regional ocean simulations of an idealized coastal upwelling system. We also present an efficient method for estimating the mean upwelling source depth. Furthermore, we show that the standard deviation of the upwelling source depth distribution increases with increasing wind stress and decreases with increasing stratification. These results can be applied to better understand and predict how coastal upwelling sites and their surface properties have and will change in past and future climates.
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  • 16
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    Unbekannt
    American Meteorological Society
    In:  EPIC3Journal of Climate, American Meteorological Society, 37(6), pp. 2059-2080, ISSN: 0894-8755
    Publikationsdatum: 2024-04-22
    Beschreibung: Heat stress is projected to intensify with global warming, causing significant socioeconomic impacts and threatening human health. Wet-bulb temperature (WBT), which combines temperature and humidity effects, is a useful indicator for assessing regional and global heat stress variability and trends. However, the variations of European WBT and their underlying mechanisms remain unclear. Using observations and reanalysis datasets, we demonstrate a remarkable warming of summer WBT during the period 1958–2021 over Europe. Specifically, the European summer WBT has increased by over 1.08C in the past 64 years. We find that the increase in European summer WBT is driven by both near-surface warming temperatures and increasing atmospheric moisture content. We identify four dominant modes of European summer WBT variability and investigate their linkage with the large-scale atmospheric circulation and sea surface temperature anomalies. The first two leading modes of the European WBT variability exhibit prominent interdecadal to long-term variations, mainly driven by a circumglobal wave train and concurrent sea surface temperature variations. The last two leading modes of European WBT variability mainly show interannual variations, indicating a direct and rapid response to large-scale atmospheric dynamics and nearby sea surface temperature variations. Further analysis shows the role of global warming and changes in midlatitude circulations in the variations of summer WBT. Our findings can enhance the understanding of plausible drivers of heat stress in Europe and provide valuable insights for regional decision-makers and climate adaptation planning.
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  • 17
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    Unbekannt
    American Meteorological Society
    In:  EPIC3Journal of Climate, American Meteorological Society, 37(8), pp. 2505-2518, ISSN: 0894-8755
    Publikationsdatum: 2024-06-21
    Beschreibung: A fundamental statistic of climate variability is its spatiotemporal correlation function. Its complex structure can be concisely summarized by a frequency-dependent measure of the effective spatial degrees of freedom (ESDOF). Here we present, for the first time, frequency-dependent ESDOF estimates of global natural surface temperature variability from purely instrumental measurements, using the HadCRUT4 dataset (1850-2014). The approach is based on a newly developed method for estimating the frequency-dependent spatial correlation function from gappy data fields. Results reveal a multicomponent structure of the spatial correlation function, including a large-amplitude short-distance component (with weak time scale dependence) and a small-amplitude long-distance component (with increasing relative amplitude toward the longer time scales). Two frequency-dependent ESDOF measures are applied, each responding mainly to either of the two components. Both measures exhibit a significant ESDOF reduction from monthly to multidecadal time scales, implying an increase of the effective spatial scale of natural surface temperature fluctuations. Moreover, it is found that a good approximation to the global number of equally spaced samples needed to estimate the variance of global mean temperature is given, at any frequency, by the greater one of the two ESDOF measures, decreasing from ;130 at monthly to ;30 at multidecadal time scales. Finally, the multicomponent structure of the correlation function together with the detected ESDOF scaling properties indicate that the ESDOF reduction toward the longer time scales cannot be explained simply by diffusion acting on stochastically driven anomalies, as it might be suggested f rom simple stochastic-diffusive energy balance models.
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  • 18
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    Unbekannt
    American Meteorological Society
    In:  EPIC3Journal of Climate, American Meteorological Society, 34(18), pp. 7373-7388, ISSN: 0894-8755
    Publikationsdatum: 2024-06-21
    Beschreibung: Climate variability occurs over wide ranges of spatial and temporal scales. It exhibits a complex spatial covariance structure, which depends on geographic location (e.g., tropics vs extratropics) and also consists of a superposition of (i) components with gradually decaying positive correlation functions and (ii) teleconnections that often involve anticorrelations. In addition, there are indications that the spatial covariance structure depends on frequency. Thus, a comprehensive assessment of the spatiotemporal covariance structure of climate variability would require an extensive set of statistical diagnostics. Therefore, it is often desirable to characterize the covariance structure by a simple summarizing metric that is easy to compute from datasets. Such summarizing metrics are useful, for example, in the context of comparisons between climate models or between models and observations. Here we introduce a frequency-dependent version of a simple measure of the effective spatial degrees of freedom. The measure is based on the temporal variance of the global average of some climate variable, and its novel aspect consists in its frequency dependence. We also provide a clear geometric interpretation of the measure. Its easy applicability is demonstrated using near-surface temperature and precipitation fields obtained from a paleoclimate model simulation. This application reveals a distinct scaling behavior of the spatial degrees of freedom as a function of frequency, ranging from monthly to millennial scales.
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  • 19
    Publikationsdatum: 2024-05-29
    Beschreibung: NORP-SORP Workshop on Polar Fresh Water: Sources, Pathways and Impacts of Freshwater in Northern and Southern Polar Oceans and Seas (SPICE-UP) What: Up to 60 participants at a time and more than twice as many registrants in total from 20 nations and across experience levels met to discuss the current status of research on freshwater in both polar regions, future directions, and synergies between the Arctic and Southern Ocean research communities When: 19–21 September 2022 Where: Online
    Repository-Name: EPIC Alfred Wegener Institut
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  • 20
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    Unbekannt
    American Meteorological Society
    In:  EPIC3Bulletin of the American Meteorological Society, American Meteorological Society, 104(9), pp. s1-s10, ISSN: 0003-0007
    Publikationsdatum: 2024-05-29
    Beschreibung: 〈jats:title〉Abstract〈/jats:title〉 〈jats:p〉—J. BLUNDEN, T. BOYER, AND E. BARTOW-GILLIES〈/jats:p〉 〈jats:p〉Earth’s global climate system is vast, complex, and intricately interrelated. Many areas are influenced by global-scale phenomena, including the “triple dip” La Niña conditions that prevailed in the eastern Pacific Ocean nearly continuously from mid-2020 through all of 2022; by regional phenomena such as the positive winter and summer North Atlantic Oscillation that impacted weather in parts the Northern Hemisphere and the negative Indian Ocean dipole that impacted weather in parts of the Southern Hemisphere; and by more localized systems such as high-pressure heat domes that caused extreme heat in different areas of the world. Underlying all these natural short-term variabilities are long-term climate trends due to continuous increases since the beginning of the Industrial Revolution in the atmospheric concentrations of Earth’s major greenhouse gases.〈/jats:p〉 〈jats:p〉In 2022, the annual global average carbon dioxide concentration in the atmosphere rose to 417.1±0.1 ppm, which is 50% greater than the pre-industrial level. Global mean tropospheric methane abundance was 165% higher than its pre-industrial level, and nitrous oxide was 24% higher. All three gases set new record-high atmospheric concentration levels in 2022.〈/jats:p〉 〈jats:p〉Sea-surface temperature patterns in the tropical Pacific characteristic of La Niña and attendant atmospheric patterns tend to mitigate atmospheric heat gain at the global scale, but the annual global surface temperature across land and oceans was still among the six highest in records dating as far back as the mid-1800s. It was the warmest La Niña year on record. Many areas observed record or near-record heat. Europe as a whole observed its second-warmest year on record, with sixteen individual countries observing record warmth at the national scale. Records were shattered across the continent during the summer months as heatwaves plagued the region. On 18 July, 104 stations in France broke their all-time records. One day later, England recorded a temperature of 40°C for the first time ever. China experienced its second-warmest year and warmest summer on record. In the Southern Hemisphere, the average temperature across New Zealand reached a record high for the second year in a row. While Australia’s annual temperature was slightly below the 1991–2020 average, Onslow Airport in Western Australia reached 50.7°C on 13 January, equaling Australia's highest temperature on record.〈/jats:p〉 〈jats:p〉While fewer in number and locations than record-high temperatures, record cold was also observed during the year. Southern Africa had its coldest August on record, with minimum temperatures as much as 5°C below normal over Angola, western Zambia, and northern Namibia. Cold outbreaks in the first half of December led to many record-low daily minimum temperature records in eastern Australia.〈/jats:p〉 〈jats:p〉The effects of rising temperatures and extreme heat were apparent across the Northern Hemisphere, where snow-cover extent by June 2022 was the third smallest in the 56-year record, and the seasonal duration of lake ice cover was the fourth shortest since 1980. More frequent and intense heatwaves contributed to the second-greatest average mass balance loss for Alpine glaciers around the world since the start of the record in 1970. Glaciers in the Swiss Alps lost a record 6% of their volume. In South America, the combination of drought and heat left many central Andean glaciers snow free by mid-summer in early 2022; glacial ice has a much lower albedo than snow, leading to accelerated heating of the glacier. Across the global cryosphere, permafrost temperatures continued to reach record highs at many high-latitude and mountain locations.〈/jats:p〉 〈jats:p〉In the high northern latitudes, the annual surface-air temperature across the Arctic was the fifth highest in the 123-year record. The seasonal Arctic minimum sea-ice extent, typically reached in September, was the 11th-smallest in the 43-year record; however, the amount of multiyear ice—ice that survives at least one summer melt season—remaining in the Arctic continued to decline. Since 2012, the Arctic has been nearly devoid of ice more than four years old.〈/jats:p〉 〈jats:p〉In Antarctica, an unusually large amount of snow and ice fell over the continent in 2022 due to several landfalling atmospheric rivers, which contributed to the highest annual surface mass balance, 15% to 16% above the 1991–2020 normal, since the start of two reanalyses records dating to 1980. It was the second-warmest year on record for all five of the long-term staffed weather stations on the Antarctic Peninsula. In East Antarctica, a heatwave event led to a new all-time record-high temperature of −9.4°C—44°C above the March average—on 18 March at Dome C. This was followed by the collapse of the critically unstable Conger Ice Shelf. More than 100 daily low sea-ice extent and sea-ice area records were set in 2022, including two new all-time annual record lows in net sea-ice extent and area in February.〈/jats:p〉 〈jats:p〉Across the world’s oceans, global mean sea level was record high for the 11th consecutive year, reaching 101.2 mm above the 1993 average when satellite altimetry measurements began, an increase of 3.3±0.7 over 2021. Globally-averaged ocean heat content was also record high in 2022, while the global sea-surface temperature was the sixth highest on record, equal with 2018. Approximately 58% of the ocean surface experienced at least one marine heatwave in 2022. In the Bay of Plenty, New Zealand’s longest continuous marine heatwave was recorded.〈/jats:p〉 〈jats:p〉A total of 85 named tropical storms were observed during the Northern and Southern Hemisphere storm seasons, close to the 1991–2020 average of 87. There were three Category 5 tropical cyclones across the globe—two in the western North Pacific and one in the North Atlantic. This was the fewest Category 5 storms globally since 2017. Globally, the accumulated cyclone energy was the lowest since reliable records began in 1981. Regardless, some storms caused massive damage. In the North Atlantic, Hurricane Fiona became the most intense and most destructive tropical or post-tropical cyclone in Atlantic Canada’s history, while major Hurricane Ian killed more than 100 people and became the third costliest disaster in the United States, causing damage estimated at $113 billion U.S. dollars. In the South Indian Ocean, Tropical Cyclone Batsirai dropped 2044 mm of rain at Commerson Crater in Réunion. The storm also impacted Madagascar, where 121 fatalities were reported.〈/jats:p〉 〈jats:p〉As is typical, some areas around the world were notably dry in 2022 and some were notably wet. In August, record high areas of land across the globe (6.2%) were experiencing extreme drought. Overall, 29% of land experienced moderate or worse categories of drought during the year. The largest drought footprint in the contiguous United States since 2012 (63%) was observed in late October. The record-breaking megadrought of central Chile continued in its 13th consecutive year, and 80-year record-low river levels in northern Argentina and Paraguay disrupted fluvial transport. In China, the Yangtze River reached record-low values. Much of equatorial eastern Africa had five consecutive below-normal rainy seasons by the end of 2022, with some areas receiving record-low precipitation totals for the year. This ongoing 2.5-year drought is the most extensive and persistent drought event in decades, and led to crop failure, millions of livestock deaths, water scarcity, and inflated prices for staple food items.〈/jats:p〉 〈jats:p〉In South Asia, Pakistan received around three times its normal volume of monsoon precipitation in August, with some regions receiving up to eight times their expected monthly totals. Resulting floods affected over 30 million people, caused over 1700 fatalities, led to major crop and property losses, and was recorded as one of the world’s costliest natural disasters of all time. Near Rio de Janeiro, Brazil, Petrópolis received 530 mm in 24 hours on 15 February, about 2.5 times the monthly February average, leading to the worst disaster in the city since 1931 with over 230 fatalities.〈/jats:p〉 〈jats:p〉On 14–15 January, the Hunga Tonga-Hunga Ha'apai submarine volcano in the South Pacific erupted multiple times. The injection of water into the atmosphere was unprecedented in both magnitude—far exceeding any previous values in the 17-year satellite record—and altitude as it penetrated into the mesosphere. The amount of water injected into the stratosphere is estimated to be 146±5 Terragrams, or ∼10% of the total amount in the stratosphere. It may take several years for the water plume to dissipate, and it is currently unknown whether this eruption will have any long-term climate effect.〈/jats:p〉
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  • 21
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    American Meteorological Society
    In:  EPIC3Bulletin of the American Meteorological Society, American Meteorological Society, 104(9), pp. s271-s321, ISSN: 0003-0007
    Publikationsdatum: 2024-05-29
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  • 22
    Publikationsdatum: 2024-06-28
    Beschreibung: 〈jats:title〉Abstract〈/jats:title〉 〈jats:p〉This study quantifies the state-of-the-art in the rapidly growing field of seasonal Arctic sea ice prediction. A novel multi-model dataset of retrospective seasonal predictions of September Arctic sea ice is created and analyzed, consisting of community contributions from 17 statistical models and 17 dynamical models. Prediction skill is compared over the period 2001–2020 for predictions of Pan-Arctic sea ice extent (SIE), regional SIE, and local sea ice concentration (SIC) initialized on June 1, July 1, August 1, and September 1. This diverse set of statistical and dynamical models can individually predict linearly detrended Pan-Arctic SIE anomalies with skill, and a multi-model median prediction has correlation coefficients of 0.79, 0.86, 0.92, and 0.99 at these respective initialization times. Regional SIE predictions have similar skill to Pan-Arctic predictions in the Alaskan and Siberian regions, whereas regional skill is lower in the Canadian, Atlantic, and Central Arctic sectors. The skill of dynamical and statistical models is generally comparable for Pan-Arctic SIE, whereas dynamical models outperform their statistical counterparts for regional and local predictions. The prediction systems are found to provide the most value added relative to basic reference forecasts in the extreme SIE years of 1996, 2007, and 2012. SIE prediction errors do not show clear trends over time, suggesting that there has been minimal change in inherent sea ice predictability over the satellite era. Overall, this study demonstrates that there are bright prospects for skillful operational predictions of September sea ice at least three months in advance.〈/jats:p〉
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  • 23
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4455-4461 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 24
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4477-4484 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 25
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4499-4503 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 26
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4582-4586 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 27
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4597-4602 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 28
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4636-4642 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 29
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4643-4650 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 30
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4714-4727 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 31
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4738-4744 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 32
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4785-4792 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 33
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4909-4911 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 34
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4920-4925 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 35
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4942-4948 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 36
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4338-4345 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 37
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4265-4272 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 38
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4299-4306 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 39
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4330-4337 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 40
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4360-4368 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 41
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4387-4400 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 42
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4418-4419 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 43
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4425-4426 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 44
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3525-3531 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 45
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3571-3576 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 46
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3631-3637 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 47
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3689-3699 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 48
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3721-3723 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 49
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5154-5159 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 50
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5139-5153 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 51
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5164-5169 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 52
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5160-5163 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 53
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3792-3793 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 54
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 2776-2778 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 55
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3596-3602 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 56
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5185-5200 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 57
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5201-5207 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 58
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3647-3661 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 59
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3700-3706 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 60
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3724-3728 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 61
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3744-3761 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 62
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 2771-2775 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 63
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 2808-2813 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 64
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 2840-2847 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 65
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 2892-2897 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 66
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 2912-2921 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 67
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 2102-2107 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 68
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 2971-2979 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 69
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3002-3011 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 70
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3045-3055 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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.
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  • 71
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5313-5315 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 72
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5324-5328 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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.
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  • 73
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5329-5334 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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.
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  • 74
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5316-5323 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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.
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  • 75
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5335-5342 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 76
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5343-5351 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 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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  • 77
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5359-5364 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: State-to-state charge–transfer cross sections have been computed for N+2(X;v=0,1,2) +Ar at 12 collision energies between 1.2 and 320 eV. A classical path method is used, whereby the vibronic degrees of freedom are treated quantum mechanically as the system moves along a classical trajectory. The calculations use the potential energy surfaces computed by Archirel and Levy. Comparison is made with experimental results for this system, including the recent work from Ng's laboratory. In most cases the agreement is quite good. There is, however, a significant difference in the charge–transfer branching ratios to produce Ar+(2P3/2) or Ar+(2P1/2) products. Possible explanations of the discrepancy are discussed. As expected, the cross sections obey the Franck–Condon principle at energies above 200 eV.
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  • 78
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5352-5358 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Second virial coefficients as function of temperature are computed for the title molecular systems interacting with He, Ne, and Ar. The relevant anisotropic forces are obtained via accurate potential functions tested earlier through the analysis of several, different properties of the various systems. The relevant quantum corrections are also computed, in addition to the classical results, and their effects analyzed vis à vis the available experimental data. The influence of such corrections on the very low-T behavior of the virial coefficients and on the determination of the Boyle temperatures is also shown and discussed. All examined potential functions are found to yield B(T) values in rather good accord with experiments, in spite of their marked differences in anisotropic behavior and in the shape of their potential well regions.
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  • 79
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5365-5373 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The reaction between ground state atomic oxygen and acetylene was studied using the crossed molecular beam method with an average collision energy of 6 kcal/mol. The two major primary reaction channels are (a) formation of CH2 and CO and (b) formation of HCCO and H. Product angular distributions and time-of-flight spectra were measured and the translational energy release was determined for each channel. The reaction proceeds primarily on the triplet surface through a long-lived intermediate. For both channels the translational energy distributions were found to peak at about 30% of the total available energy, indicating the existence of an exit channel barrier in each case. The branching ratio between channel (a) and (b) was found to be 1.4±0.5.
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  • 80
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5387-5391 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: A pump-and-probe technique is utilized to yield a population distribution over the rotational quantum states of the nascent product MgH in the reaction of Mg(1P1) and H2. The resulting normalized profile of the MgH bimodal distribution at 693 K coincides with that at 733 K, as well as with the results obtained at 380 K by Breckenridge and co-workers. This temperature dependence demonstrates that the bimodality actually results from the insertive reaction alone. This conclusion is consistent with the isotopic effect.
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  • 81
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5374-5386 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Oscillations with large amplitudes (〉500 K), high frequencies (〉8 Hz), and good reproducibility are observed in methylamine decomposition on electrically heated Pt, Rh, and Ir wires at pressures of 0.25–8.0 Torr and temperatures between 900 and 1500 K. The major reaction involves formation of HCN which is endothermic by 37 kcal/mol, so that the reaction strongly cools the wire, which counteracts resistive heating. A photodiode array was used to monitor spatial and temporal oscillations with resolutions of 1 mm and 30 Hz, respectively. On Pt, the frequency increased with increasing pressure and with decreasing wire diameter, while amplitude was a weak function of these parameters. On Ir, oscillations were more complex with regions of the wire often oscillating independently and more variability between experiments. However, the overall behavior resembles that on Pt. On Rh, frequencies were much lower (〈0.03 Hz), oscillations occurred over a smaller temperature range and halves of the wire frequently oscillated out of phase with each other. Oscillatory behavior of methylamine decomposition on Pt was modeled by a simple lumped model which gives semiquantitative agreement with observations. The model assumes a simple unimolecular reaction with CH3NH2 adsorption blocked at low temperatures by formation of a strongly adsorbed CN which is known to be very stable on Pt (Ed (approximately-equal-to)50 kcal/mol). Calculated frequencies, pressure dependencies, amplitudes, and temperature range of oscillations agree quite well with experiments using reasonable values for adsorption and reaction rate parameters, and wire geometry and properties.
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  • 82
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5402-5411 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: A method to deconvolute experimental differential cross sections is presented. The procedure removes the effect of the angular divergence of the primary beam, the finite size of the detector, and multiple scattering. The resulting cross section is the optimal experimental result. The method also determines ε=nlQ0, the average number of times each beam particle is scattered. Here n is the number density of scattering gas, l is the length of the scattering region, and Q0 is the true absolute cross section. If the product nl is known, Q0 can be determined. Since the effect of the finite angular resolution of the apparatus has been removed, this method should yield accurate total cross sections. This, in turn, allows the differential cross section to be put on an absolute scale.
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  • 83
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5392-5401 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Quenching of highly excited vibrational states of NO2 in baths of CO2, N2O, and CO has been investigated. Dilute NO2 mixtures were excited by a pulse from an excimer pumped dye laser operating at 495 nm. The ν3 antisymmetric stretching modes of CO2 (2349 cm−1) and N2O (2223 cm−1) and the v=1 level of CO (2143 cm−1) were probed with continuous wave IR diode lasers. The amount of energy transferred from excited NO2 to the ν3 modes of both CO2 and N2O was found to be 3%±1% of the original excitation energy. On the other hand, a smaller amount of energy (0.9%±0.3%) was deposited into the CO vibrational mode for NO2 contained in a dilute CO bath. These results support a picture of very inefficient transfer from high energy states of donor molecules to the high-frequency vibrational modes of small bath molecules. Differences in the efficiency of energy reception by the high-frequency modes of these three molecules scale roughly as the infrared transition moments for the bath states indicating the importance of resonance effects in the energy transfer process, but a combination of short- and long-range force mechanisms is probably necessary to account for the observed differences.
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  • 84
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5412-5424 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The rate constant of a bimolecular gas-phase chemical reaction is determined by the energy distribution of the reactants and the cross section for the reaction. Systems in which photolysis and other nonequilibrium processes occur may have energy distributions which differ significantly from the equilibrium distribution. Analytical solutions are derived for the rate constant as a function of temperature for certain systems in which nonequilibium processes occur. The analytical solutions are compared with the numerical solutions and the agreement is found to be excellent, confirming the validity of the approximations that were made. Chemical reactions are simulated with the Monte Carlo method and the results again confirm the validity of the analytical solutions. Under certain nonequilibrium conditions, it is shown that the complex expression for the rate constant as a function of temperature reduces to a simple form, which resembles the Arrhenius equation. In this special case, the dependence of the results on the shape of the reaction cross section is investigated.
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  • 85
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5440-5443 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: In a recent paper it was shown that rare gas ions form bound molecular states which decay by emission of radiation in the VUV. They are potential candidates as storage media for VUV lasers. In the present investigation the ions Kr+K, Kr+Cs, Xe+K, and Xe+Cs are produced by electron beam excitation of suitable gas mixtures with He as buffer gas. Studies of the reaction kinetics were performed for Kr+K. The rate constant for the reaction Kr++K+He was determined to be 2.8×10−30 cm3 s−1. Kr+K is strongly quenched by plasma electrons and by reaction with Kr. The fluorescence yield at intense excitation was determined to be about 5×10−2 VUV quanta per He+ ion.
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  • 86
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 2124-2139 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Raman scattering in liquid (and in some cases in solid) isotopic mixtures of HC1 and DC1 is analyzed to prove recent theories by Bratos and Tarjus [Phys. Rev. A 32, 2431 (1985)], Logan [Mol. Phys. 58, 97 (1986)], and Knapp [J. Chem. Phys. 81, 643 (1984)] on vibrational line broadening in liquids. The concentration and temperature dependencies of isotropic [Ji(ω)] and anisotropic [Ja(ω)] line shapes have been studied between triple point (Tt) and critical temperature (Tc). It has been found that in accordance with the Bratos–Tarjus theory, Ji (ω) is much more sensitive of isotopic composition of the liquid than Ja(ω). An analysis of the concentration dependence of the broadening parameters near Tt illustrates the importance of cross correlations between the environmental broadening and the resonant intermolecular coupling. The spectral activity of three-particle resonant transfer also becomes significant. From the change of the maximum of Ji(ω) with isotopic dilution, which is a linear function of mole fraction, the dipole moment derivative δμ/δq is estimated to be more than twice that of its gas phase value. The asymmetry of the isotropic bands of both HC1 and DC1 changes with concentration at constant temperature. With increasing temperature, Ji(ω) of pure and diluted samples narrows as T−0.5 and T−0.3, respectively. Ji(ω) has been found to be intermediate between the slow and the fast modulation limit. From the high frequency wing of Ji (ω) the time constant of the zeroth order memory function was obtained. Its activation energy increases with increasing T. This is in qualitative agreement with the temperature dependence of the Enskog collision time and the spin–rotational correlation time. Taking into account the results of the Bratos–Tarjus theory, orientational correlation times τ(2) are determined from Ja (ω). The Raman method yields τ(2) values which are twice as long as those determined from NMR relaxation.
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  • 87
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1734-1753 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Theoretical investigations of the outer valence doubly ionized states of ethylene are presented using ab initio Green's function and configuration interaction methods. The vertical double ionization potentials computed by the Green's function method using the ADC(2) scheme are discussed in connection with the Auger spectrum of ethylene and found to reproduce the experimental spectrum quite accurately. Another main purpose of the present work is the investigation of the potential energy surfaces of selected states via ADC(2) and the study of the nuclear dynamics on them. It is shown that only the ground state of the dication is nonplanar with a torsional angle of 90°. The investigation of the topology of the surfaces reveals a low energy conical intersection of the dicationic ground and first excited states. The associated vibronic coupling problem turns out to include, additionally, the second excited state and thus, we encounter here a three-state problem. In the approximation of linear vibrational and vibronic coupling the static and dynamic aspects of the vibronic interaction are investigated by a model Hamiltonian comprising three nonseparable nondegenerate vibrational modes. The input data for the model are extracted from the ADC(2) results. With the aid of this Hamiltonian we have computed a hypothetical "sudden'' double ionization spectrum of ethylene whose complex structure is analyzed stepwise and by cuts through the pertinent adiabatic and diabatic surfaces. The analysis exhibits that the conical intersection of the two lower lying states dominates the vibronic dynamics and leads to strong vibronic mixing between them. This mixing is indirectly reinforced by the interaction between the intermediate and the upper states. As a consequence, strong nonadiabatic effects occur in the ethylene dication. Furthermore, two of the three surfaces involved in the conical intersection are also involved in a multidimensional avoided crossing. A more detailed analysis presented earlier has exhibited that the states belong to an interesting class where two potential energy surfaces are likely not to coincide although plenty of nuclear degrees of freedom exist, in principle, to allow for an intersection to occur.
    Materialart: Digitale Medien
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  • 88
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1789-1795 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The recently introduced annihilated unrestricted Hartree–Fock (AUHF) wave function—in which the first spin contaminant in an unrestricted Hartree–Fock (UHF) wave function has been annihilated self-consistently—is discussed in some detail with particular attention to its use as a basis for a perturbation expansion. A series of calculations are presented highlighting the advantages and disadvantages of a second-order Møller–Plesset (AUMP2) perturbation treatment.
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  • 89
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1813-1823 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: A study is made of the vibrational energy levels and the corresponding oscillation dynamics of the clusters Xe4He2, Xe3He2, and I24He. XeHe2 is a representative of the "three ball'' clusters, while I2He is a prototype of the "stick and ball'' systems. The treatment is based on the vibrational self-consistent field (SCF) method, which introduces an approximate separation of the modes involved. Success of the method depends on an adequate choice of the coordinates that are being mutually separated. We use physical arguments, based on mass ratios and potential function considerations, as well as comparative SCF calculations in different coordinate systems, to determine the appropriate modes for each system. Numerically exact results are also obtained by configuration interaction (CI) calculations using a basis of SCF states. The SCF and CI calculations include all modes and employ realistic potentials. Several states that are both rotationally and vibrationally excited are also calculated. The main conclusions are: (1) Hyperspherical coordinates are the best modes for XeHe2; ellipsoidal coordinates are best for I2He. In each case, the "good modes'' SCF gives energies in remarkable agreement with the exact (CI) ones. (2) XeHe2 resembles a quantum liquid drop: Even in the ground state, it is delocalized over and between the (two) classical equilibrium structures. (3) Structural distributions, rather than rigid geometry, are essential for the description of such floppy clusters. The single-mode SCF wave functions offer a highly accurate description of the structural distributions. (4) There is a sequence of bound, excited rotational states of I2He in which the He precesses around the I2 axis. The amplitude of the I2He bending vibrations are very large (θA〈20°), but none of the bound states involves a full rotational motion around the I2 stick (with angular momentum normal to the axis). The SCF method with the "good coordinates'' proposed here is expected to yield results of similar high accuracy for any cluster of the "three balls'' or "stick and ball'' types.
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  • 90
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1702-1705 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: A new implementation of the complex coordinate method is presented. It is a combination of the stabilization method with the partitioning technique, supplemented with the idea of dilation-adapted basis sets. This method is designed to handle large scale calculations of many-electron resonant states, as to minimize the amount of complex arithmetics and in particular to avoid the diagonalization of the complex eigenvalue problem. Both a resonant eigenvalue and a corresponding eigenvector are obtained. An application to the lowest doubly excited autoionizing states of helium is presented.
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  • 91
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1918-1925 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: We use the mean field theory of Pink et al. with the ab initio calculations of the density of states of Tevlin et al. to calculate various features of the main phase transition of a lipid bilayer using fewer fitting parameters than in previous models. Good agreement with experiment is obtained for the calculated transition temperature, Gibbs free energy, enthalpy, and average number of gauche rotations per acyl chain. The average chain area is poorly predicted; we expect this to be corrected once cooperative packing of the acyl chains is taken into account. The nematic order along the chain is also calculated and found to agree qualitatively with experiment.
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  • 92
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1938-1940 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 93
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1937-1938 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The photoreduction of CH3Cl was used to detect the transmission of electrons through layers of H2O and Xe on Ni(111) under ultrahigh vacuum (UHV) conditions. At a laser wavelength of 248 nm with H2O spacers, the electron intensity exhibited a nearly exponential decay to zero signal with the 1/e point at about 2 monolayers. At 193 nm with H2O spacers, the signal decayed with the 1/e point at about 4 monolayers to a constant value due to the direct photofragmentation of the CH3 Cl possible at this wavelength. At 248 nm with Xe spacers, the signal decayed by a factor of 4 in the first 2 monolayers, after which the signal was nearly constant and nonzero for at least 64 monolayers, indicating a long electron mean free path. CH3Br is shown to behave similarly with H2 O spacers at 248 nm.
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  • 94
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1944-1945 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: We observed for the first time in an optical high resolution experiment (fluorescence line narrowing) the coupling of low frequency adsorbate motions to vibronic bands of the electronic transition of quinizarin adsorbed on γ-alumina. These motions may provide an important dephasing mechanism for the electronic excitation of absorbed molecules. The increased hole width of adsorbed dyes which is several times larger than in amorphous hosts is thought to be caused by these low frequency modes.
    Materialart: Digitale Medien
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  • 95
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1012-1014 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Oxalic acid can produce oscillations in the Belousov–Zhabotinsky-type reaction in a closed batch system without a mechanism for bromine removal. The stirring rate has a significant effect on the reaction.
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  • 96
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1631-1642 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: In this paper we explore the interrelationship between the energetics and the thermodynamic properties of molecular clusters. We advance simple models for the energy spectrum, which are used to derive analytical results for the thermodynamic properties of these clusters. The energy spectrum is characterized by the distribution of the energies of the local minima of the nuclear potential energy hypersurface, i.e., the inherent structures. On each of these energy levels the vibrational density of states of the particular inherent structure is superimposed. The energy spectra were specified in terms of the energy gap, Δ, between the (single) ground state and the excited-state inherent structures, the number, R, of the inherent structures and their energetic spread W. Four classes of energy spectra were considered. (1) A large energy gap with nearly degenerate excited-state manifold, i.e., Δ(very-much-greater-than)W. (2) A large energy gap with a considerable spread of the excited-state manifold, i.e., Δ(very-much-less-than)W and W/R(very-much-less-than)Δ. (3) A gapless spectrum with W/R(approximately-greater-than)Δ. (4) A multiple bunched spectrum with several energy gaps. Explicit analytical relations for the temperature dependence of the internal energy were derived for energy spectra of types (1), (2), and (3) both for the canonical and for the microcanonical ensembles. For energy spectra of types (1) and (2) the caloric curve exhibits a single inflection, which marks the "transition''. A unified description of multistate isomerization with large R, which corresponds to rare-gas clusters, and of molecular isomerization with R(approximately-equal-to)1, which prevails for alkali-halide clusters, was provided. For energy spectra of type (3) the transition disappears, while for energy spectra of type (4) hierarchical isomerization is exhibited. Our analytical models have established the ensemble dependence of the transition for types (1) and (2), which is manifested by a considerable broadening of the transition range for the canonical ensemble, reflecting the role of energy fluctuations in the finite system.
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  • 97
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5694-5700 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The photopolymerization properties and the surface pressure dependence of excitonic absorption of polydiacetylene (PDA), i.e., poly-(heptacosa-10,12-diynoic acid), are investigated by in situ reflection spectra of a monolayer at a N2 gas–water (pure water, CdCl2 aqueous solution) interface. The electronic structure of the initially appearing PDA is strongly dependent on the packing condition of diacetylene monomer, the blue- and red-form PDAs that initially appear in loose and close packing conditions, respectively. A reversible color change induced by a change in surface pressure is found for the first time in a partially polymerized PDA monolayer on pure water, in which blue and red form PDAs appear predominantly at low and high surface pressures, respectively. Further, two metastable phases, observed at wavelengths about 40 nm longer than those of the blue form, are thought to be induced by the rheological process of the substitutional sidegroups. Our results suggest that these color changes are closely related to a strain on the acetylenic backbone structure which is induced by the deformation of substitutional alkyl sidegroups.
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  • 98
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5701-5706 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The adsorption of NO on Ag(111) at 80 K has been studied by high resolution electron energy loss spectroscopy (HREELS) and thermal desorption spectroscopy (TDS). At low exposures (≤0.05 L) NO is adsorbed in part dissociatively and in part molecularly in two different threefold bridge states (in upright and bent or tilted orientation with respect to the surface normal). The NO molecules in the threefold bridge position are desorbed at 100 K. With increasing exposure the desorption temperature shifts gradually to 110 K. At medium exposures (∼0.13 L) additional NO is adsorbed molecularly in an atop position with an upright orientation in admixture with atomic N and O and molecular NO adsorbed in threefold bridge states. The NO molecules adsorbed in atop position are weakly bonded on the surface and are desorbed at about 90 K. Simultaneously, N2O is formed and adsorbed on the surface. At saturation a new bent or tilted NO species in atop position appears on the surface and the amount of N2O significantly increases. The N2O molecules are desorbed at 90, 110, and 190 K. At saturation all the NO and NO-derived species (the threefold bridge and atop states, N2O and atomic oxygen and nitrogen) coexist on Ag(111).
    Materialart: Digitale Medien
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  • 99
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1762-1774 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Nonrelativistic and relativistic Hartree–Fock (HF) and configuration interaction (CI) calculations have been performed in order to analyze the relativistic and correlation effects in various diatomic gold compounds. It is found that relativistic effects reverse the trend in most molecular properties down the group (11). The consequences for gold chemistry are described. Relativistic bond stabilizations or destabilizations are dependent on the electronegativity of the ligand, showing the largest bond destabilization for AuF (86 kJ/mol at the CI level) and the largest stabilization for AuLi (−174 kJ/mol). Relativistic bond contractions lie between 1.09 (AuH+) and 0.16 A(ring) (AuF). Relativistic effects of various other properties are discussed. A number of as yet unmeasured spectroscopic properties, such as bondlengths (re), dissociation energies (De), force constants (ke), and dipole moments (μe), are predicted.
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  • 100
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1783-1788 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Geometry optimizations and band structure calculations are reported on two polymeric vinylene derivatives of pyrene: poly(1,6-pyrenylene vinylene) and poly(2,7-pyrenylene vinylene). The results are indicative of a dramatic sensitivity of the electronic structure on the mode of connection of the two vinylene units to the pyrene rings, in agreement with the chemist's intuition. An analysis of the atomic π orbital contributions to the one-electron wave functions shows that the HOMO–LUMO characteristics of both compounds are markedly different. The 1-6 mode of connection leads to an electronic structure similar to that of polyparaphenylene with a bandgap of 2.9 eV. The 2-7 mode of connection results in a significantly lower bandgap, around 1.7 eV, due to the stabilization of quinoid resonance structures.
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