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Article
A Comprehensive Analysis in Terms of Molecule-Intrinsic, Quasi- Atomic Orbitals. II. Strongly Correlated MCSCF Wave Functions
Journal of Physical Chemistry A
  • Aaron C. West, Iowa State University
  • Michael Schmidt, Iowa State University
  • Mark S. Gordon, Iowa State University
  • Klaus Ruedenberg, Iowa State University
Document Type
Article
Disciplines
Publication Version
Published Version
Publication Date
9-1-2015
DOI
10.1021/acs.jpca.5b03399
Abstract

A methodology is developed for the quantitative identification of the quasi-atomic orbitals that are embedded in a strongly correlated molecular wave function. The wave function is presumed to be generated from configurations in an internal orbital space whose dimension is equal to (or slightly larger) than that of the molecular minimal basis set. The quasi-atomic orbitals are found to have large overlaps with corresponding orbitals on the free atoms. They separate into bonding and nonbonding orbitals. From the bonding quasi-atomic orbitals, localized bonding and antibonding molecular orbitals are formed. The resolution of molecular density matrices in terms of these orbitals furnishes a basis for analyzing the interatomic bonding patterns in molecules and the changes in these bonding patterns along reaction paths. A new bond strength measure, the kinetic bond order, is introduced.

Comments

Reprinted (adapted) with permission from Journal of Physical Chemistry A 119 (2015): 10360, doi:10.1021/acs.jpca.5b03399. Copyright 2015 American Chemical Society.

Copyright Owner
American Chemical Society
Language
en
File Format
application/pdf
Citation Information
Aaron C. West, Michael Schmidt, Mark S. Gordon and Klaus Ruedenberg. "A Comprehensive Analysis in Terms of Molecule-Intrinsic, Quasi- Atomic Orbitals. II. Strongly Correlated MCSCF Wave Functions" Journal of Physical Chemistry A Vol. 119 Iss. 41 (2015) p. 10360 - 10367
Available at: http://works.bepress.com/mark_gordon/338/