The maximum occupancy condition for the localized property-optimized orbitals

Abstract

It is shown analytically that the Chemist's Localized Property-optimized Orbitals (CLPOs), which are the localized orbitals obtainable from the results of ab initio calculations by the open-source program JANPA (http://janpa.sourceforge.net/) according to the recently proposed optimal property partitioning condition, form the Lewis structure with nearly maximum possible total electron occupancy. The conditions required for this additional optimality to hold are discussed. In particular, when a single-determinant wavefunction is used to describe the molecular system without a noticeable electron delocalization, CLPOs derived from this wavefunction approximately optimize the same target quantity as the Natural Bond Orbitals (NBOs), establishing in this way the link between the two sets of localized orbitals. The performance of CLPO and NBO methods is compared by using a dataset containing 7101 small molecules, and the relevant methodological features of both methods are discussed.