Modified electronic population analysis for transition-metal complexes

A modification to the Mulliken electronic population analysis designed primarily for use on transition-metal systems is presented. All terms arising from the metal basis functions including diagonal terms are repartioned between the metal and the ligands. This reapportionment is an attempt to reflect more accurately the actual electron density in well-defined areas of space, which characterize the metal and the ligand. This modified analysis appears to yield more reasonable charge assignments than a conventional Mulliken analysis. The cost of the analysis is negligible in comparison with that of calculating the wave function.