Modern valence bond theory

Electronic structure methods
Valence bond theory
Coulson–Fischer theory
Generalized valence bond
Modern valence bond theory
Molecular orbital theory
Hartree–Fock method
Semi-empirical quantum chemistry methods
Møller–Plesset perturbation theory
Configuration interaction
Coupled cluster
Multi-configurational self-consistent field
Quantum chemistry composite methods
Quantum Monte Carlo
Density functional theory
Time-dependent density functional theory
Thomas–Fermi model
Orbital-free density functional theory
Linearized augmented-plane-wave method
Projector augmented wave method
Electronic band structure
Nearly free electron model
Tight binding
Muffin-tin approximation
k·p perturbation theory
Empty lattice approximation
GW approximation
Korringa–Kohn–Rostoker method

Modern valence bond theory is the application of valence bond theory (VBT) with computer programs that are competitive in accuracy and economy, with programs for the Hartree–Fock or post-Hartree-Fock methods. The latter methods dominated quantum chemistry from the advent of digital computers because they were easier to program. The early popularity of valence bond methods thus declined. It is only recently that the programming of valence bond methods has improved. These developments are due to and described by Gerratt, Cooper, Karadakov and Raimondi (1997);[1] Li and McWeeny (2002); Joop H. van Lenthe and co-workers (2002);[2] Song, Mo, Zhang and Wu (2005); and Shaik and Hiberty (2004)[3]

While molecular orbital theory (MOT) describes the electronic wavefunction as a linear combination of basis functions that are centered on the various atoms in a species (linear combination of atomic orbitals), VBT describes the electronic wavefunction as a linear combination of several valence bond structures.[4] Each of these valence bond structures can be described using linear combinations of either atomic orbitals, delocalized atomic orbitals (Coulson-Fischer theory), or even molecular orbital fragments.[5] Although this is often overlooked, MOT and VBT are equally valid ways of describing the electronic wavefunction, and are actually related by a unitary transformation. Assuming MOT and VBT are applied at the same level of theory, this relationship ensures that they will describe the same wavefunction, but will do so in different forms.[4]

  1. ^ Cite error: The named reference Gerratt1997 was invoked but never defined (see the help page).
  2. ^ van Lenthe, J. H.; Dijkstra, F.; Havenith, R. W. A. TURTLE - A gradient VBSCF Program Theory and Studies of Aromaticity. In Theoretical and Computational Chemistry: Valence Bond Theory; Cooper, D. L., Ed.; Elsevier: Amsterdam, 2002; Vol. 10; pp 79--116.
  3. ^ See further reading section.
  4. ^ a b Hiberty, Philippe C.; Braïda, Benoît (2018-05-22). "Pleading for a Dual Molecular‐Orbital/Valence‐Bond Culture". Angewandte Chemie International Edition. 57 (21): 5994–6002. doi:10.1002/anie.201710094. ISSN 1433-7851. PMID 29244907.
  5. ^ Shaik, Sason; Hiberty, Philippe C. (2007-11-16). A Chemist's Guide to Valence Bond Theory. Hoboken, NJ, USA: John Wiley & Sons, Inc. doi:10.1002/9780470192597. ISBN 978-0-470-19259-7.