Superposition of waves or densities : Which is the nature of chemical resonance?
© 2020 Wiley Periodicals LLC.
| Veröffentlicht in: | Journal of computational chemistry. - 1984. - 42(2021), 6 vom: 05. März, Seite 412-417 |
|---|---|
| 1. Verfasser: | |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2021
|
| Zugriff auf das übergeordnete Werk: | Journal of computational chemistry |
| Schlagworte: | Journal Article chemical bonding natural resonance theory resonance theory valence bond theory wave function analysis |
| Zusammenfassung: | © 2020 Wiley Periodicals LLC. Resonance is a fundamental and widely used concept in chemistry, but there exist two distinct theories of chemical resonance, based on quite different and incompatible premises: the wave-function-based resonance theory (WFRT), assuming the superposition of wave functions, versus the density-matrix-based resonance theory (DMRT), which interprets the resonance phenomenon as the superposition of density matrices. The latter theory, best known to the chemistry community as the natural resonance theory (NRT), has received much more popularity than the WFRT. In this contribution, the DMRT is shown to be inherently inadequate: (i) the exact density matrix expansion is mathematically impossible unless unphysical negative weights are introduced; (ii) any approximate density matrix representing the resonance hybrid lacks the idempotent property. Therefore, the validity of the NRT ansatz should be seriously questioned. The WFRT seems the only reasonable explanation of resonance so far, and has been shown to provide valuable insights into diverse chemical problems |
|---|---|
| Beschreibung: | Date Revised 08.10.2021 published: Print-Electronic CommentIn: J Comput Chem. 2021 Jul 15;42(19):1338-1340. - PMID 34041769 Citation Status PubMed-not-MEDLINE |
| ISSN: | 1096-987X |
| DOI: | 10.1002/jcc.26463 |