A valence bond study of the dioxygen molecule
Copyright (c) 2006 Wiley Periodicals, Inc.
| Veröffentlicht in: | Journal of computational chemistry. - 1984. - 28(2007), 1 vom: 15. Jan., Seite 185-97 |
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| 1. Verfasser: | |
| Weitere Verfasser: | , , , |
| Format: | Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2007
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| Zugriff auf das übergeordnete Werk: | Journal of computational chemistry |
| Schlagworte: | Journal Article Research Support, Non-U.S. Gov't Solutions Oxygen S88TT14065 |
| Zusammenfassung: | Copyright (c) 2006 Wiley Periodicals, Inc. The dioxygen molecule has been the subject of valence bond (VB) studies since 1930s, as it was considered as the first "failure" of VB theory. The object of this article is to provide an unambiguous VB interpretation for the nature of chemical bonding of the molecule by means of modern VB computational methods, VBSCF, BOVB, and VBCI. It is shown that though the VBSCF method can not provide quantitative accuracy for the strongly electronegative and electron-delocalized molecule because of the lack of dynamic correlation, it still gives a correct qualitative analysis for wave function of the molecule and provides intuitive insights into chemical bonding. An accurate quantitative description for the molecule requires higher levels of VB methods that incorporate dynamic correlation. The potential energy curves of the molecule are computed at the various VB levels. It is shown that there exists a small hump in the PECs of VBSCF for the ground state, as found in previous studies. However, higher levels of VB methods dissolve the hump. The BOVB and VBCI methods reproduce the dissociation energies and other physical properties of the ground state and the two lowest excited states in very good agreement with experiment and with sophisticated MO based methods, such as the MRCI method |
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| Beschreibung: | Date Completed 25.01.2007 Date Revised 21.11.2013 published: Print Citation Status MEDLINE |
| ISSN: | 1096-987X |