Cooper, David L 
ORCID: 0000-0003-0639-0794, Penotti, Fabio E and Karadakov, Peter B
(2023)
Reassessing the Composition of Hybrid Orbitals in Contemporary VB Calculations.
JOURNAL OF PHYSICAL CHEMISTRY A, 127 (23).
pp. 4949-4956.
Abstract
Large variations in the ratios between the p and s components of individual hybrid orbitals that have been observed in contemporary ab initio VB calculations are reassessed, and links are established to specific energy terms that drive bond formation. It is demonstrated that the ratios between the p and s components for individual hybrid orbitals are not indicative of the overall hybridization status of the relevant atom, which exhibits only relatively small variations with the level of theory, irrespective of whether or not non-dynamical and dynamical electron correlation effects are accounted for. An alternative orbital representation that turns out to be far more consistent with the overall hybridization of the relevant atom is examined. The chosen test cases, which can be compared with the classical sp<sup>3</sup>, sp<sup>2</sup>, and sp hybridization models for a central carbon atom, are CH<sub>4</sub> (T<sub><i>d</i></sub>), trigonal CH<sub>3</sub> (D<sub>3<i>h</i></sub>), and triplet CH<sub>2</sub> distorted from its ground state geometry so as to be linear (D<sub>∞<i>h</i></sub>).
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | CH₄, CH₃ and CH₂, hybridization, interatomic kinetic energy, localized natural orbitals (LNOs), spin-coupled generalized valence bond (SCGVB) |
| Divisions: | Faculty of Science and Engineering > School of Physical Sciences |
| Depositing User: | Symplectic Admin |
| Date Deposited: | 01 Jun 2023 08:27 |
| Last Modified: | 13 Jul 2023 04:24 |
| DOI: | 10.1021/acs.jpca.3c01857 |
| Open Access URL: | https://dx.doi.org/10.1021/acs.jpca.3c01857 |
| Related URLs: | |
| URI: | https://livrepository.liverpool.ac.uk/id/eprint/3170775 |
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