Spin-Coupled Generalized Valence Bond Theory: New Perspectives on the Electronic Structure of Molecules and Chemical Bonds

Dunning, Thom H Jr, Xu, Lu T, Cooper, David L ORCID: 0000-0003-0639-0794 and Karadakov, Peter B (2021) Spin-Coupled Generalized Valence Bond Theory: New Perspectives on the Electronic Structure of Molecules and Chemical Bonds. JOURNAL OF PHYSICAL CHEMISTRY A, 125 (10). pp. 2021-2050.

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Abstract

Spin-Coupled Generalized Valence Bond (SCGVB) theory provides the foundation for a comprehensive theory of the electronic structure of molecules. SCGVB theory offers a compelling orbital description of the electronic structure of molecules as well as an efficient and effective zero-order wave function for calculations striving for quantitative predictions of molecular structures, energetics, and other properties. The orbitals in the SCGVB wave function are usually semilocalized, and for most molecules, they can be interpreted using concepts familiar to all chemists (hybrid orbitals, localized bond pairs, lone pairs, etc.). SCGVB theory also provides new perspectives on the nature of the bonds in molecules such as C₂, Be₂ and SF₄/SF₆. SCGVB theory contributes unparalleled insights into the underlying cause of the first-row anomaly in inorganic chemistry as well as the electronic structure of organic molecules and the electronic mechanisms of organic reactions. The SCGVB wave function accounts for nondynamical correlation effects and, thus, corrects the most serious deficiency in molecular orbital (RHF) wave functions. Dynamical correlation effects, which are critical for quantitative predictions, can be taken into account using the SCGVB wave function as the zero-order wave function for multireference configuration interaction or coupled cluster calculations.

Item Type:	Article
Depositing User:	Symplectic Admin
Date Deposited:	15 Feb 2021 08:10
Last Modified:	18 Jan 2023 23:27
DOI:	10.1021/acs.jpca.0c10472
Related URLs:	Author Publisher
URI:	https://livrepository.liverpool.ac.uk/id/eprint/3104673