1996/02/05 by Roman F. Nalewajski, Janusz Mrozek · 9 citations
Chemistry · Physics and Astronomy · Materials Science · #Crystallography and molecular interactions #Advanced Chemical Physics Studies #Thermal and Kinetic Analysis
paper · doi:10.1002/(sici)1097-461x(1996)57:3<377::aid-qua11>3.0.co;2-1
The recently introduced set of quadratic ionic and covalent valence indices from changes in the pair-diagonal part of the molecular (Hartree-Fock) two-electron density matrix, ΔΓ(2)(a, b) (orthogonal atomic orbital [OAO] basis set), relative to separated atoms limit (SAL), is extended to cubic valence numbers; they are calculated from the corresponding changes in the three-electron density matrix, ΔΓ(3)(a,b,c). The two- and three-electron indices are given by the corresponding contributions to ΔΓ(2), and ΔΓ(3), which are quadratic and cubic in terms of relevant changes in the one-electron density matrix. The new valence measures are partitioned into one-, two-, and three-center contributions comprising purely ionic (covalent) and mixed ionic-covalent terms. For integral OAO occupations in the SAL, the sum of all three-electron contributions vanishes exactly in the UHF approximation; for fractional occupations, they give rise to a rather small correction to the overall two-electron valence index. The properties of cubic valence numbers are tested on a model three-orbital description of a symmetric (ABA), collinear transition state and on the OQ2 (Q = 1,0, −1) and O2(bond)H+ systems. Preliminary results for B2H6 are also given. © 1996 John Wiley & Sons, Inc.