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A Comprehensive Analysis in Terms of Molecule-Intrinsic,Quasi-Atomic Orbitals. II. Strongly Correlated MCSCF Wave Functions.

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Title: A Comprehensive Analysis in Terms of Molecule-Intrinsic,Quasi-Atomic Orbitals. II. Strongly Correlated MCSCF Wave Functions.
Authors: West, Aaron C.1, Schmidt, Michael W.1, Gordon, Mark S.1, Ruedenberg, Klaus1
Source: Journal of Physical Chemistry A. Oct2015, Vol. 119 Issue 41, p10360-10367. 8p.
Subjects: Atomic orbitals, Multi-configurational self-consistent field method, Wave functions, Interatomic angles, Molecular orbitals
Abstract: A methodology is developed for thequantitative identificationof the quasi-atomic orbitals that are embedded in a strongly correlatedmolecular wave function. The wave function is presumed to be generatedfrom configurations in an internal orbital space whose dimension isequal to (or slightly larger) than that of the molecular minimal basisset. The quasi-atomic orbitals are found to have large overlaps withcorresponding orbitals on the free atoms. They separate into bondingand nonbonding orbitals. From the bonding quasi-atomic orbitals, localizedbonding and antibonding molecular orbitals are formed. The resolutionof molecular density matrices in terms of these orbitals furnishesa basis for analyzing the interatomic bonding patterns in moleculesand the changes in these bonding patterns along reaction paths. Anew bond strength measure, the kinetic bond order, is introduced. [ABSTRACT FROM AUTHOR]
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Abstract:A methodology is developed for thequantitative identificationof the quasi-atomic orbitals that are embedded in a strongly correlatedmolecular wave function. The wave function is presumed to be generatedfrom configurations in an internal orbital space whose dimension isequal to (or slightly larger) than that of the molecular minimal basisset. The quasi-atomic orbitals are found to have large overlaps withcorresponding orbitals on the free atoms. They separate into bondingand nonbonding orbitals. From the bonding quasi-atomic orbitals, localizedbonding and antibonding molecular orbitals are formed. The resolutionof molecular density matrices in terms of these orbitals furnishesa basis for analyzing the interatomic bonding patterns in moleculesand the changes in these bonding patterns along reaction paths. Anew bond strength measure, the kinetic bond order, is introduced. [ABSTRACT FROM AUTHOR]
ISSN:10895639
DOI:10.1021/acs.jpca.5b03399