A RIGOROUS ENERGY PARTITIONING SCHEME FOR ANALYSIS OF MOLECULAR-INTERACTIONS

Citation
M. Martinov et J. Cioslowski, A RIGOROUS ENERGY PARTITIONING SCHEME FOR ANALYSIS OF MOLECULAR-INTERACTIONS, Molecular physics, 85(1), 1995, pp. 121-129
Citations number
38
Categorie Soggetti
Physics, Atomic, Molecular & Chemical
Journal title
ISSN journal
00268976
Volume
85
Issue
1
Year of publication
1995
Pages
121 - 129
Database
ISI
SICI code
0026-8976(1995)85:1<121:AREPSF>2.0.ZU;2-C
Abstract
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.