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Photodissociation dynamics of the pyridinyl radical: Time-dependent quantum wave-packet calculations.
- Source :
-
Journal of Chemical Physics . 2017, Vol. 146 Issue 12, p1-12. 12p. 3 Diagrams, 6 Charts, 10 Graphs. - Publication Year :
- 2017
-
Abstract
- The H-atom photodissociation reaction from the pyridinyl radical (C5H5NH) via the low-lying πσ* excited electronic state is investigated by nonadiabatic time-dependent quantum wave-packet dynamics calculations. A model comprising three electronic states and three nuclear coordinates has been constructed using ab initio multi-configurational self-consistent-field and multi-reference perturbation theory methods. Two conical intersections among the three lowest electronic states have been characterized in the framework of the linear vibronic-coupling model. Time-dependent wave-packet simulations have been performed using the multi-configuration time-dependent Hartree method. The population dynamics of the diabatic and adiabatic electronic states and the time-dependent dissociation behavior are analyzed for various vibrational initial conditions. The results provide detailed mechanistic insight into the photoinduced H-atom dissociation process from a hypervalent aromatic radical and show that an efficient dissociation reaction through two conical intersections is possible. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00219606
- Volume :
- 146
- Issue :
- 12
- Database :
- Academic Search Index
- Journal :
- Journal of Chemical Physics
- Publication Type :
- Academic Journal
- Accession number :
- 122027338
- Full Text :
- https://doi.org/10.1063/1.4978283