A transferable H sub(2)O interaction potential based on a single center multipole expansion: SCME

A transferable potential energy function for describing the interaction between water molecules is presented. The electrostatic interaction is described rigorously using a multipole expansion. Only one expansion center is used per molecule to avoid the introduction of monopoles. This single center a...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2013-09, Vol.15 (39), p.16542-16556
Main Authors: Wikfeldt, K T, Batista, E R, Vila, F D, Jonsson, H
Format: Article
Language:English
Subjects:
Approximation
Dispersions
Electrostatics
Mathematical analysis
Multipoles
Phases
Simulation
Water
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Summary:A transferable potential energy function for describing the interaction between water molecules is presented. The electrostatic interaction is described rigorously using a multipole expansion. Only one expansion center is used per molecule to avoid the introduction of monopoles. This single center approach turns out to converge and give close agreement with ab initiocalculations when carried out up to and including the hexadecapole. Both dipole and quadrupole polarizability are included. All parameters in the electrostatic interaction as well as the dispersion interaction are taken from ab initiocalculations or experimental measurements of a single water molecule. The repulsive part of the interaction is parametrized to fit ab initiocalculations of small water clusters and experimental measurements of ice I sub(h). The parametrized potential function was then used to simulate liquid water and the results agree well with experiment, even better than simulations using some of the point charge potentials fitted to liquid water. The evaluation of the new interaction potential for condensed phases is fast because point charges are not present and the interaction can, to a good approximation, be truncated at a finite range.
ISSN:1463-9076
1463-9084
DOI:10.1039/c3cp52097h