| Autor: |
Dunning TH Jr; Department of Chemistry, University of Washington, Seattle, Washington 98195-1700, United States., Xu LT; Department of Chemistry, University of Washington, Seattle, Washington 98195-1700, United States., Cooper DL; Department of Chemistry, University of Liverpool, Liverpool, L69 7ZD, U.K., Karadakov PB; Department of Chemistry, University of York, York, YO10 5DD, U.K. |
| Jazyk: |
angličtina |
| Zdroj: |
The journal of physical chemistry. A [J Phys Chem A] 2021 Mar 18; Vol. 125 (10), pp. 2021-2050. Date of Electronic Publication: 2021 Mar 06. |
| DOI: |
10.1021/acs.jpca.0c10472 |
| Abstrakt: |
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 C 2 , Be 2 and SF 4 /SF 6 . 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. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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