TITLE

The observation of strong pseudo-Jahn–Teller activity in the benzene cation B 2E2g state

AUTHOR(S)
Goode, Jon G.; Hofstein, Jason D.; Johnson, Philip M.
PUB. DATE
August 1997
SOURCE
Journal of Chemical Physics;8/8/1997, Vol. 107 Issue 6, p1703
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
Photoinduced Rydberg ionization (PIRI) spectroscopy has been applied to the problem of recording vibrationally resolved spectra of the dipole-forbidden B 2E2g←X 2E1g transition of C6H6+ and C6D6+. PIRI spectra of the B state have been recorded via a number of vibrational states of the ionic ground state. A combination of Herzberg–Teller and pseudo-Jahn–Teller vibronic coupling between the B state and a close lying C state were used to explain the complex B state vibrational structure. The two pseudo-Jahn–Teller vibrational modes, ν16 and ν17, were both found to be active in the PIRI spectra. In addition, evidence for a strong pseudo-Jahn–Teller interaction within each of these modes was found. The perturbed vibronic bands resulting from this pseudo-Jahn–Teller activity were successfully modeled using a two-mode pseudo-Jahn–Teller vibronic coupling model. Using a combination of the spectral results and the pseudo-Jahn–Teller calculations, we were able to generate absolute vibronic symmetry assignments for many of the lower B state vibrational levels, from which vibrational assignments were made. The calculations also produced unperturbed vibrational frequencies for both pseudo-Jahn–Teller active modes along with values for their respective linear coupling constants. © 1997 American Institute of Physics.
ACCESSION #
33899311

 

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