Key role of the polarization anisotropy of water in modeling classical polarizable force fields.
We have evaluated the extent to which classical polarizable force fields, based either on the chemical potential equalization principle or on distributed polarizabilities in the framework of the Sum of Interactions Between Fragments Ab initio computed (SIBFA), can reproduce the ab initio polarization energy and the dipole moment of three distinct water oligomers: bifurcated chains, transverse hydrogen-bonded chains, and longitudinal hydrogen-bonded chains of helical shape. To analyze the many-body polarization effect, chains of different size, i.e., from 2 to 12 water monomers, have been considered. Although the dipole moment is a well-defined quantity in both classical polarizable models and quantum mechanical methods, polarization energy can be defined unequivocally only in the former type of approaches. In this study we have used the Kitaura-Morokuma (KM) procedure. Although the KM approach is on the one hand known to overestimate the polarization energy for strongly interacting molecules, on the other hand it can account for the many-body polarization effectively, whereas some other procedures do not. Our data show that, if off-centered lone pair polarizabilities are explicitly represented, classical polarizable force fields can afford a close agreement with the ab initio results, both in terms of polarization energy and in terms of dipole moment.
Piquemal
Jean-Philip
JP
Laboratoire de Chimie Théorique, Université Pierre et Marie Curie (Paris VI), case 137, 4 place Jussieu, 75252 Paris Cedex 05, France. jpp@lct.jussieu.fr
Chelli
Riccardo
R
Procacci
Piero
P
Gresh
Nohad
N
D008962:Models, Theoretical; D014867:Water / Q000737:chemistry*
D014867:Water