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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 98 (1993), S. 5337-5351 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The spectra of van der Waals trimers formed from two atoms and a diatomic molecule are investigated. A computational method for calculating vibrational energies, rotational constants and angular expectation values for such complexes is developed and applied to the Ar2–HCl complex. All five low-frequency modes of the trimer are included. The pair potentials for Ar–Ar and Ar–HCl interactions are well known, and calculations are performed on Ar2–HCl potentials obtained from them assuming pairwise additivity. The calculations are compared with experimental results obtained from microwave and far-infrared spectroscopy. Substantial discrepancies between experiment and theory are found, and are attributed to the effects of nonadditive interactions. Several different contributions to the nonadditive interactions are investigated: dispersion forces, electrostatic induction forces, and exchange overlap forces are all found to be significant, but not large enough to explain the discrepancies. Exchange multipole forces, arising from the interaction between overlap-induced multipoles on the Ar atoms and the permanent multipoles on the HCl molecule, are found to be important, and to improve the agreement between experiment and theory substantially. It seems likely that it will be possible to obtain detailed information on nonadditive interactions from the spectroscopy of van der Waals trimers.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 98 (1993), S. 2160-2169 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Several different methods for calculating the energy levels of van der Waals trimers are compared for the case of Ar3. These include solution of the coupled equations in a basis set of hyperspherical harmonics and various three-dimensional basis set expansions. It is found that a basis set expansion in Jacobi coordinates gives results that are adequate for calculating the energy levels of the lowest few vibrational states, and that this method is computationally cheap enough to be extended to handle atom–atom–diatom complexes. The transition dipole moments for the lowest allowed transitions of Ar3 are estimated, and found to be about 7×10−5 D. The effects of three-body forces on the energy levels are investigated, and found to be large enough to determine from high-resolution spectroscopic experiments.
    Type of Medium: Electronic Resource
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  • 3
    Publication Date: 2022-01-31
    Description: Highlights • Novel multi-disciplinary approach to tracing freshwater and particle transport into boundary currents; • Significant glacial inputs reach coastal waters and are transported rapidly offshore; • Low surface water dissolved silicon concentrations maintained by diatom activity despite strong glacial and benthic supplies. Abstract Biogeochemical cycling in high-latitude regions has a disproportionate impact on global nutrient budgets. Here, we introduce a holistic, multi-disciplinary framework for elucidating the influence of glacial meltwaters, shelf currents, and biological production on biogeochemical cycling in high-latitude continental margins, with a focus on the silica cycle. Our findings highlight the impact of significant glacial discharge on nutrient supply to shelf and slope waters, as well as surface and benthic production in these regions, over a range of timescales from days to thousands of years. Whilst biological uptake in fjords and strong diatom activity in coastal waters maintains low dissolved silicon concentrations in surface waters, we find important but spatially heterogeneous additions of particulates into the system, which are transported rapidly away from the shore. We expect the glacially-derived particles – together with biogenic silica tests – to be cycled rapidly through shallow sediments, resulting in a strong benthic flux of dissolved silicon. Entrainment of this benthic silicon into boundary currents may supply an important source of this key nutrient into the Labrador Sea, and is also likely to recirculate back into the deep fjords inshore. This study illustrates how geochemical and oceanographic analyses can be used together to probe further into modern nutrient cycling in this region, as well as the palaeoclimatological approaches to investigating changes in glacial meltwater discharge through time, especially during periods of rapid climatic change in the Late Quaternary.
    Type: Article , PeerReviewed
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    Format: text
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