M. Martinov et J. Cioslowski, A RIGOROUS ENERGY PARTITIONING SCHEME FOR ANALYSIS OF MOLECULAR-INTERACTIONS, Molecular physics, 85(1), 1995, pp. 121-129
A rigorous method for partitioning the molecular interaction energy in
to classical electrostatic, charge-transfer, and wavefunction relaxati
on contributions is proposed. The energy components, defined with quan
tities central to density functional theory, are calculated with the h
elp of the topological theory of atoms in molecules. Since the new sch
eme does not rely on Hilbert space partitioning, it is applicable to a
ny level of electronic structure theory and it yields energy component
s that are true observables converging smoothly at the limit of a comp
lete basis set. For this reason, the new method does not possess the d
eficiencies of the previously introduced Morokuma-Kitaura and Glendeni
ng-Streitwieser approaches. The results of several test calculations a
re compared with those obtained with the other energy partitioning sch
emes and found to exhibit superior numerical stability with respect to
the quality of basis sets.