Ab initio surface hopping excited-state molecular dynamics approach on the basis of spin-orbit coupled states : An application to the A-band photodissociation of CH3 I
© 2018 Wiley Periodicals, Inc.
| Veröffentlicht in: | Journal of computational chemistry. - 1984. - 40(2019), 2 vom: 15. Jan., Seite 456-463 |
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| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2019
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| Zugriff auf das übergeordnete Werk: | Journal of computational chemistry |
| Schlagworte: | Journal Article nonadiabatic coupling photodissociation spin-orbit coupling surface hopping AIMD |
| Zusammenfassung: | © 2018 Wiley Periodicals, Inc. Ab initio molecular dynamics approach has been extended to multi-state dynamics on the basis of the spin-orbit coupled electronic states that are obtained through diagonalization of the spin-orbit coupling matrix with the multi-state second-order multireference perturbation theory energies in diagonal elements and the spin-orbit coupling terms at the state-averaged complete active space self-consistent field level in off-diagonal elements. Nonadiabatic transitions over the spin-orbit coupled states were taken into account explicitly by a surface hopping scheme with utilizing the nonadiabatic coupling terms calculated by numerical differentiation of the spin-orbit coupled wavefunctions and analytical nonadiabatic coupling terms. The present method was applied to the A-band photodissociation of methyl iodide, CH3 I + hv → CH3 + I (2 P3/2 )/I* (2 P1/2 ), for which a pioneering theoretical work was reported by Amatatsu, Yabushita, and Morokuma. The present results reproduced well the experimental branching ratio and energy distributions in the dissociative products. © 2018 Wiley Periodicals, Inc |
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| Beschreibung: | Date Revised 20.11.2019 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
| ISSN: | 1096-987X |
| DOI: | 10.1002/jcc.25727 |