title: A Comprehensive Analysis in Terms of Molecule-Intrinsic, Quasi-Atomic Orbitals. II. Strongly Correlated MCSCF Wave Functions.
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.
authors.affiliation: Department of Chemistry and Ames Laboratory USDOE, Iowa State University , Ames, Iowa 50011, United States.
authors.forename: Aaron C
authors.initials: AC
authors.lastname: West
authors.affiliation: Department of Chemistry and Ames Laboratory USDOE, Iowa State University , Ames, Iowa 50011, United States.
authors.forename: Michael W
authors.initials: MW
authors.lastname: Schmidt
authors.affiliation: Department of Chemistry and Ames Laboratory USDOE, Iowa State University , Ames, Iowa 50011, United States.
authors.forename: Mark S
authors.initials: MS
authors.lastname: Gordon
authors.affiliation: Department of Chemistry and Ames Laboratory USDOE, Iowa State University , Ames, Iowa 50011, United States.
authors.forename: Klaus
authors.initials: K
authors.lastname: Ruedenberg