Direct configuration interaction and multiconfigurational self-consistent-field method for multiple active spaces with variable occupations. I. Method

Abstract

In order to reduce the number of ineffective configurations in a priori generated configuration spaces, a direct configuration interaction method has been developed which limits the electron occupations of orbital groups making up a total active space. A wave function is specified by first partitioning an active space into an unrestricted number of orbital groups and second by providing limiting values, in the form of minima and maxima, for the electron occupancies of each group. The configuration interaction problem corresponding to all possible determinants satisfying these conditions is solved in a fully direct manner by the use of Slater–Condon expressions in conjunction with single and double replacements. This configuration interaction approach, termed occupation restricted multiple active space-configuration interaction, has also been linked with orbital optimization programs to produce the occupation restricted multiple active space-self consistent field method.