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Multi-mode vibronic interactions in the five lowest electronic states of the fluorobenzene radical cation
Abstract
The multi-mode vibronic interactions between the five lowest electronic states of the fluorobenzene radical cation are investigated theoretically, based on ab initio electronic structure data, and employing the linear vibronic coupling model. Low-energy conical intersections, and strong vibronic couplings are found to prevail within the set of X-A and B-C-D cationic states, while the interactions between these two sets of states are found to be rather weak (owing to high-energy conical intersections). The overall intensity distribution of the experimental photoelectron spectrum, as well as the line positions observed in the MATI spectrum, are well reproduced. The vibronic interactions in the X-A states are found to be a replica of the multi-mode dynamical Jahn–Teller effect in the parent system, the ground state X^2E_1g of the benzene radical cation. Ultrafast internal conversion processes within the electronic manifolds in question demonstrate the strength of the nonadiabatic coupling effects and complement the analogous findings for the electronic spectra. The implications for the fluorescence dynamics of the fluorobenzene radical cation are discussed.
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Authors (4)
-
Ioan Bâldea
- Eötvös Loránd University Institute of Chemistry
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Péter Szalay
- Universität Heidelberg Physikalisch-Chemisches Institut
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Horst Köppel
- Universität Heidelberg Physikalisch-Chemisches Institut
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Details
- Category:
- Articles
- Type:
- artykuł w czasopiśmie wyróżnionym w JCR
- Published in:
-
CHEMICAL PHYSICS
no. 329,
edition 1-3,
pages 65 - 75,
ISSN: 0301-0104 - Language:
- English
- Publication year:
- 2006
- Bibliographic description:
- Bâldea I., Franz J., Szalay P., Köppel H.: Multi-mode vibronic interactions in the five lowest electronic states of the fluorobenzene radical cation// CHEMICAL PHYSICS. -Vol. 329, iss. 1-3 (2006), s.65-75
- DOI:
- Digital Object Identifier (open in new tab) 10.1016/j.chemphys.2006.07.025
- Verified by:
- Gdańsk University of Technology
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