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dc.contributor.authorWang, Xiao-Gangen
dc.contributor.authorCarrington, Tucker Jren
dc.contributor.authorBajaj, Pushpen
dc.contributor.authorPaesani, Francescoen
dc.date.accessioned2018-01-04T13:52:01Z
dc.date.available2018-01-04T13:52:01Z
dc.date.issued2017-12-30
dc.identifier.otherhttps://doi.org/10.1063/1.5005540
dc.identifier.urihttp://hdl.handle.net/1974/23816
dc.description.abstractFull-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.en
dc.language.isoenen
dc.subjectIonic Clustersen
dc.subjectVibrational Spectroscopyen
dc.subjectIon Water Interactionsen
dc.titleVibrational Spectra of Halide-Water Dimers: Insights on Ion Hydration from Full-Dimensional Quantum Calculations on Many-Body Potential Energy Surfacesen
dc.typejournal articleen


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