Multi-mode vibronic interactions in the five lowest electronic states of the fluorobenzene radical cation

Ioan Bâldea, Jan Franz, P. Szalay, Horst Köppel

Research output: Contribution to journalArticle

26 Citations (Scopus)

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 over(X, ∼) s(-) over(A, ∼) and over(B, ∼) s(-) over(C, ∼) s(-) over(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 over(X, ∼) s(-) over(A, ∼) states are found to be a replica of the multi-mode dynamical Jahn-Teller effect in the parent system, the over(X, ∼)2 E1 g ground state 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.

Original languageEnglish
Pages (from-to)65-75
Number of pages11
JournalChemical Physics
Volume329
Issue number1-3
DOIs
Publication statusPublished - Oct 26 2006

Fingerprint

Fluorobenzenes
Electronic states
Cations
cations
intersections
electronics
Jahn-Teller effect
internal conversion
interactions
Photoelectrons
Benzene
replicas
electronic spectra
complement
Ground state
Electronic structure
photoelectrons
Fluorescence
benzene
electronic structure

Keywords

  • Conical intersection
  • Fluorobenzene
  • Multi-mode dynamics
  • Photoelectron spectrum
  • Vibronic coupling

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Atomic and Molecular Physics, and Optics

Cite this

Multi-mode vibronic interactions in the five lowest electronic states of the fluorobenzene radical cation. / Bâldea, Ioan; Franz, Jan; Szalay, P.; Köppel, Horst.

In: Chemical Physics, Vol. 329, No. 1-3, 26.10.2006, p. 65-75.

Research output: Contribution to journalArticle

Bâldea, Ioan ; Franz, Jan ; Szalay, P. ; Köppel, Horst. / Multi-mode vibronic interactions in the five lowest electronic states of the fluorobenzene radical cation. In: Chemical Physics. 2006 ; Vol. 329, No. 1-3. pp. 65-75.
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