An efficient generalized polyelectron population analysis in orbital spaces: the hole-expansion methodology

We present relations leading to an efficient generalized population analysis in orbital spaces of usual delocalized molecular orbital wave functions. Besides the calculation of the diagonal elements of the reduced density matrices of any order, one can also calculate efficiently the probabilities (or, in general, the weights) of various occupation schemes of local electronic structures, by using generalized density operators referring to both electrons and electron holes. Within this population analysis, correlated molecular orbital wave functions can be used, and there are no restrictions to the number of the analyzed electrons and electron holes. It is based on the hole-expansion methodology, according to which a given electronic population is expanded in terms involving only electron holes, which as shown, can be calculated very efficiently; usual difficulties arising from the necessity to handle extremely large local determinantal basis sets are avoided, without introducing approximations. Although an emphasis is given for populations in the basis of orthogonal orbital spaces (providing probabilities), the case of nonorthogonal ones is also considered in order to show the connection of the generalized populations and the traditional weights obtained from valence-bond wave functions. Physically meaningful populations can be obtained by using natural orbitals, such as the natural atomic orbitals (NAOs) (orthogonal orbitals) or the pre-NAO's (nonorthogonal orbitals); numerical applications for pyrrole molecule are presented in the basis of these natural orbitals.