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First-Principles Many-Body Nonadditive Polarization Energies from Monomer and Dimer Calculations Only: A Case Study on Water
journal contribution
posted on 2019-12-10, 19:44 authored by Rory A.
J. Gilmore, Martin T. Dove, Alston J. MisquittaThe many-body polarization energy is the major source
of nonadditivity
in strongly polar systems such as water. This nonadditivity is often
considerable and must be included, if only in an average manner, to
correctly describe the physical properties of the system. Models for
the polarization energy are usually parametrized using experimental
data, or theoretical estimates of the many-body effects. Here we show
how many-body polarization models can be developed for water complexes
using data for the monomer and dimer only using ideas recently developed
in the field of intermolecular perturbation theory and state-of-the-art
approaches for calculating distributed molecular properties based
on the iterated stockholder atoms (ISA) algorithm. We show how these
models can be calculated, and we validate their accuracy in describing
the many-body nonadditive energies of a range of water clusters. We
further investigate their sensitivity to the details of the polarization
damping models used. We show how our very best polarization models
yield many-body energies that agree with those computed with coupled-cluster
methods, but at a fraction of the computational cost.
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many-body energiespolarization energyDimer CalculationsISAmany-body polarization energywater complexesFirst-Principles Many-Body Nonadditive Polarization Energiesiterated stockholder atomsmany-body polarization modelspolarization modelswater clustersnonadditivitycoupled-cluster methodsdatamany-body nonadditive energiesCase Studymany-body effectsperturbation theory
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