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    Vibrational Spectra of Halide-Water Dimers: Insights on Ion Hydration from Full-Dimensional Quantum Calculations on Many-Body Potential Energy Surfaces

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    Date
    2017-12-30
    Author
    Wang, Xiao-Gang
    Carrington, Tucker Jr
    Bajaj, Pushp
    Paesani, Francesco
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    Abstract
    Full-dimensional vibrational spectra are calculated for both X (H2O) and X (D2O) dimers (X = F, Cl,

    Br, I) at the quantum-mechanical level. The calculations are carried out on two sets of recently developed

    potential energy functions (PEFs), namely, Thole-type model energy (TTM-nrg) and many-body

    energy (MB-nrg), using the symmetry-adapted Lanczos algorithm with a product basis set including

    all six vibrational coordinates. Although both TTM-nrg and MB-nrg PEFs are derived from

    coupled-cluster single double triple-F12 data obtained in the complete basis set limit, they differ

    in how many-body effects are represented at short range. Specifically, while both models describe

    long-range interactions through the combination of two-body dispersion and many-body classical electrostatics,

    the relatively simple Born-Mayer functions employed in the TTM-nrg PEFs to represent

    short-range interactions are replaced in the MB-nrg PEFs by permutationally invariant polynomials

    to achieve chemical accuracy. For all dimers, the MB-nrg vibrational spectra are in close agreement

    with the available experimental data, correctly reproducing anharmonic and nuclear quantum

    effects. In contrast, the vibrational frequencies calculated with the TTM-nrg PEFs exhibit significant

    deviations from the experimental values. The comparison between the TTM-nrg and MB-nrg results

    thus reinforces the notion that an accurate representation of both short-range interactions associated

    with electron density overlap and long-range many-body electrostatic interactions is necessary for

    a correct description of hydration phenomena at the molecular level.
    URI for this record
    http://hdl.handle.net/1974/23816
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