Symmetry-adapted perturbation theory with regularized Coulomb potential

We present a novel formulation of the symmetry-adapted perturbation theory involving a regularization of the Coulomb singularities in the interaction operator. The perturbation development is performed in two stages. At the f irst stage, we apply the weak symmetry forcing to a regularized interaction operator and, subsequently, at the second stage we treat the singular, sho rt-range part of the perturbation by employing the strong symmetry forcing characteristic of the Eisenschitz-London-Hirschfelder-van der Avoird theory . The correct asymptotics is recovered at the first stage and the residual, short-range part of the perturbation is sufficiently weakened by the symme try projection to prevent the divergence of the series appearing at the sec ond stage of our procedure. We tested the method by performing high-order c alculations of the interaction energy in the singlet and triplet states res ulting from the interaction of two ground-state hydrogen atoms. A large bas is set of Gaussian geminals was used to obtain saturated results. It is sho wn that the proposed regularization procedure eliminates the pathological c onvergence properties observed earlier for the perturbation expansions invo lving the weak symmetry forcing and gives very accurate interaction energie s in a low-order treatment of the singular part of the potential. (C) 2001 Elsevier Science B.V. All rights reserved.