Spin-Coupled Generalized Valence Bond Theory: An Appealing Orbital Theory of the Electronic Structure of Atoms and Molecules

Dunning, Thom H, Cooper, David L ORCID: 0000-0003-0639-0794, Xu, Lu T and Karadakov, Peter B (2024) Spin-Coupled Generalized Valence Bond Theory: An Appealing Orbital Theory of the Electronic Structure of Atoms and Molecules. In: Comprehensive Computational Chemistry. Elsevier, pp. 354-402. ISBN 9780128232569

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Official URL: http://dx.doi.org/10.1016/b978-0-12-821978-2.00017...

Abstract

This chapter outlines the basic elements of Spin-Coupled Generalized Valence Bond (SCGVB) theory, including optimization and analysis of SCGVB wavefunctions. It is shown how such wavefunctions, which account for non-dynamical electron correlation, provide compelling descriptions of the electronic structures of the ground and excited states of molecules and of the electronic mechanisms of molecular reactions, using as representative examples: the “traditional” HCN molecule, and its fragmentation into CH and N; the formation of “hypervalent” SF₄; resonance/antiresonance in benzene and C₇H₇⁺; excited states of CH and of O₃/SO₂; and the reaction of triplet methylene with H₂. Starting from a natural orbital representation of the SCGVB wavefunction, traditional multireference configuration interaction calculations are used to account for dynamical correlation effects, which are required for quantitative predictions of molecular properties.

Item Type:	Book Section
Uncontrolled Keywords:	Spin-Coupled Generalized Valence Bond (SCGVB) Theory, Atomic and Molecular Electronic Structure, Chemical Bonding, Covalent Bond, Recoupled Pair Bond, Recoupled Pair Bond Dyad, Potential Energy Curves, Potential Energy Surfaces, Resonance/Aromaticity, Antiresonance/Antiaromaticity, Excited States, Chemical Reactions, Non-dynamical Electron Correlation, Dynamical Electron Correlation
Divisions:	Faculty of Science and Engineering > School of Physical Sciences
Depositing User:	Symplectic Admin
Date Deposited:	06 Jun 2022 08:31
Last Modified:	15 Mar 2024 03:35
DOI:	10.1016/b978-0-12-821978-2.00017-9
Open Access URL:	http://dx.doi.org/10.26434/chemrxiv-2022-lxrzw-v2
Related URLs:	Publisher
URI:	https://livrepository.liverpool.ac.uk/id/eprint/3151843