A comprehensive analysis of molecule-intrinsic quasi-atomic, bonding, and correlating orbitals. I. Hartree-Fock wave functions

Through a basis-set-independent web of localizing orbital-transformations, the electronic wave function of a molecule is expressed in terms of a set of orbitals that reveal the atomic structure and the bonding pattern of a molecule. The analysis is based on resolving the valence orbital space in terms of an internal space, which has minimal basis set dimensions, and an external space. In the internal space, oriented quasi-atomic orbitals and split-localized molecular orbitals are determined by new, fast localization methods. The density matrix between the oriented quasi-atomic orbitals as well as the locations of the split-localized orbitals exhibit atomic populations and interatomic bonding patterns. A correlation-adapted quasi-atomic basis is determined in the external orbital space. The general formulations are specified in detail for Hartree-Fock wave functions. Applications to specific molecules exemplify the general scheme. (C) 2013 AIP Publishing LLC.