Calculation of the Jahn-Teller effect in benzene cation: Application to spectral analysis

Abstract

Ab initio calculations have been performed for the cations of benzene, C6H6, and its fluorinated analogs, C6F6 and C6H3F3. Calculated molecular parameters characterizing the Jahn-Teller potential energy surface (PES) are very consistent with those derived from the spectra of C6F6+ and C6H3F3+. However the calculated Jahn-Teller stabilization energy for the benzene cation is roughly three times greater than that previously reported experimentally. With the aid of the calculated values, a more complete analysis of the available spectral data for C6H6+ and C6D6+ is performed, with an emphasis on the data from ZEKE experiments and IR spectra of the Ar⋅C6H6+, Ne⋅C6H6+, and Ar⋅C6D6+ complexes. The comprehensive analysis reveals Jahn-Teller activity in 3 e2g modes for C6(H/D)6+ and provides values for their vibrational frequencies, linear and quadratic Jahn-Teller coupling constants, as well as quadratic coupling constants for several other degenerate modes. These new molecular parameters are generally in good agreement with the corresponding values derived from the ab initio calculations and produce a total Jahn-Teller stabilization energy in good agreement with the computed value.