Photophysics of fluorinated benzene. III. Hexafluorobenzene

A theoretical study of the photoabsorption spectroscopy of hexafluorobenzene (HFBz) is presented in this paper. The chemical effect due to fluorine atom substitution on the electronic structure of benzene (Bz) saturates in HFBz. State- of-the-art quantum chemistry calculations are carried out to establish potential energy surfaces and coupling surfaces of five energetically low-lying electronic (two of them are orbitally degenerate) states of HFBz. Coupling of these electronic states caused by the Jahn-Teller (JT) and pseudo-Jahn-Teller (PJT) type of interactions are examined. The impact of these couplings on the nuclear dynamics of the participating electronic states is thoroughly investigated by quantum mechanical methods and the results are compared with those observed in the experiments. The complex structure of the S(1) ← S(0) absorption band is found to originate from a very strong nonadiabatic coupling of the S(2) (of πσ* origin) and S(1) (of ππ* origin) state. While S(2) state is orbitally degenerate and JT active, the S(1) state is nondegenerate. These states form energetically low-lying conical intersections (CIs) in HFBz. These CIs are found to be the mechanistic bottleneck of the observed low quantum yield of fluorescence emission, non overlapping absorption, and emission bands of HFBz and contribute to the spectral width. Justification is also provided for the observed two peaks in the second absorption (the unassigned "c band") band of HFBz. The peaks observed in the third, fourth, and fifth absorption bands are also identified and assigned.