Calculations of nonadditive effects by means of supermolecular Mo/ller–Plesset perturbation theory approach: Ar3 and Ar4

Abstract

Nonadditive, multibody effects arising in the supermolecular Mo/ller–Plesset perturbation theory (MPPT) (IMPPT) calculations are classified and interpreted in terms of the exchange, induction, deformation, and dispersion contributions, as defined by the perturbation theory of intermolecular forces. As an example the many-body effects in the equilateral Ar trimer and tetrahedral Ar tetramer, calculated through the MP4 level of theory with extended basis [7s4p2d], are reported and discussed. It is stressed that the ‘‘Heitler–London-exchange plus dispersion’’ model for nonadditive effects is too attractive mainly because of the neglect of the second-order exchange contribution.