An approximate frozen core approach to valence only molecular calculations

Abstract

A simple valence electron-only theory based on an approximate frozen core approach and an exact core-valence strong orthogonality condition is developed for atomic and molecular systems. A unique reduced basis is introduced in which both core and valence orbitals are expanded. The core representation is roughly approximated, and the valence orbital overlap with the corresponding all-electron reference functions is nearly exact. The size of the reduced basis in terms of primitive functions is practically the same as that adopted by effective core potential methods in which the valence orbitals have the correct nodal properties. Results obtained with the present approach are presented for LiO, BeO and CaO molecules, and compared with the corresponding all-electron frozen core calculations. In addition, a detailed investigation on Li n Be clusters (n=1,..., 6) is carried out.