Nonadditive effects in HF and HCl trimers

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Abstract
Nonadditive effects are calculated for (HF)3 and (HCl)3 complexes and analyzed via the combination of perturbation theory of intermolecular forces with Mo/ller–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.