Spin-orbit Ab initio investigation of the photodissociation of dibromomethane in the gas and solution phases
Copyright 2008 Wiley Periodicals, Inc.
| Veröffentlicht in: | Journal of computational chemistry. - 1984. - 29(2008), 15 vom: 30. Nov., Seite 2513-9 |
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| Weitere Verfasser: | , , |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2008
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| Zugriff auf das übergeordnete Werk: | Journal of computational chemistry |
| Schlagworte: | Journal Article |
| Zusammenfassung: | Copyright 2008 Wiley Periodicals, Inc. A clear and reliable theoretical investigation on dibromomethane (CH(2)Br(2)) photodissociation is desired. The calculation must consider: (i) relativistic effects; (ii) the potential energy curves (PECs) of spin-orbit coupling states; (iii) geometry optimization by the method with both static and dynamic electron correlations; (iv) solvent effects on the photodissociation in the solution. All these have been considered in this study by state-of-the-art quantum chemical calculations. The experimentally observed photodissociation in the gas phase with products of spin-orbit-coupled states, Br((2)P(3/2)) and Br*((2)P(1/2)), was assigned by multi-state second order multiconfigurational perturbation theory in conjunction with spin-orbit interaction through complete active space state interaction (MS-CASPT2/CASSI-SO) PECs. The mechanisms of the experimentally observed photodissociation and photoisomerization in solvent were elucidated by the MS-CASPT2/CASSI-SO method combined with polarized continuum model of the solvent |
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| Beschreibung: | Date Completed 03.12.2008 Date Revised 01.10.2008 published: Print Citation Status PubMed-not-MEDLINE |
| ISSN: | 1096-987X |
| DOI: | 10.1002/jcc.21008 |