Document Type

Article

Journal/Book Title

Journal of Chemical Physics

Publication Date

1989

Volume

91

First Page

7048

Last Page

7056

DOI

10.1063/1.457322

Abstract

Nonadditive effects are calculated for (HF)3 and (HCl)3 complexes and analyzed via the combination of perturbation theory of intermolecular forces with Møller–Plesset perturbation theory (MPPT). In both systems the nonadditivity is dominated by the self‐consistent field (SCF) deformation effect, i.e., mutual polarization of the monomer wavefunctions. Heitler–London exchange and correlation effects are of secondary importance. Three‐body terms exhibit much lesser basis set dependence than the two‐body effects and even quite moderate basis sets which are not accurate enough for treatment of two‐body forces can yield three‐body effects of quantitative quality. This is due in large measure to the additivity of strongly basis set dependent components such as uncorrelated and correlated electrostatics and dispersion. Various approximate models for the three‐body potentials and total interaction in the (HF)3 cluster are analyzed from the point of view of their ability to predict the orientation dependence of interaction energy.

Comments

Originally published by American Institute of Physics in the Journal of Chemical Physics.

Publisher's PDF can be accessed through the remote link.

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