Frozen core and effective core potentials in symmetry-adapted perturbation theory.

The application of the frozen-core approximation (FCA) and effective core potentials (ECPs) within symmetry-adapted perturbation theory (SAPT) has been investigated and implemented. Unlike in the case of conventional electronic-structure theories, the development of a frozen-core version of SAPT is not straightforward. In particular, the FCA realizations neglecting excitations from core orbitals and restricting all summation indices to valence orbitals only are no longer equivalent. It is shown that it is necessary in SAPT to keep some terms containing products of the valence orbitals of one monomer and the core orbitals of the other one in the exchange-energy components. When these terms are included or, equivalently, the “infinite-excitation-energy” approximation omitting only the excitations from the core orbitals is used, the accuracy of the frozen-core approximation in SAPT matches that obtained in supermolecular perturbational and coupled-cluster methods. If these terms are neglected, i.e., within the “index-range-restriction” approximation, several exchange corrections are significantly underestimated. When ECPs are used in SAPT, the accuracy of the interaction energies is as good as in conventional supermolecular methods, provided that the residual supermolecular Hartree-Fock term is included. We have found that only some types of ECPs can be reliably used for calculations of interaction energies both in SAPT and in supermolecular approaches. For systems containing heavy atoms, both FCA and the use of ECPs lead to very significant savings of computer time. [ABSTRACT FROM AUTHOR]