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Computational Study on the Photophysics of Protonated Benzene

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journal contribution
posted on 21.05.2009, 00:00 by Michal F. Rode, Andrzej L. Sobolewski, Claude Dedonder, Christophe Jouvet, Otto Dopfer
The reaction paths in the lowest excited electronic states relevant for the photophysics of protonated benzene, C6H7+, have been explored by ab initio techniques of electronic structure theory. For this purpose, the first four excited singlet electronic states of C6H7+ have been calculated at the CC2/cc-pVTZ level of theory. The CC2 approach has been validated by CASPT2 and TD-DFT calculations. The calculated UV absorption spectrum is in good agreement with the experimental spectrum. It has been found that the out-of-plane and the in-plane ring deformation leads in the excited states in an essential barrierless manner to a low-lying conical intersection between the lowest excited states and with the ground state, providing a mechanism for efficient radiationless deactivation, which is expected to quench luminescence of the isolated molecular ion.