We also computed photoelectron spectra (PES) of benzene and compared them with the available experimental data. Several types of calculations were performed. First, conventional Franck-Condon factors were computed for the ground electronic states of the neutral benzene and for its cation. As a preliminary step, structure optimizations and harmonic frequency calculations were done for C 6 H 6 and C 6 H 6 + . However, C 6 H 6 + is a well known example of the Jahn-Teller effect. Therefore, the same procedures cannot be applied to the excited electronic states of C 6 H 6 + and only the first band of the PE spectrum could be obtained using this procedure. The WS procedure with harmonic modes has been used to account for vibrational motions. With this simplistic treatment of vibrational degrees of freedom in the harmonic approximation we computed an approximate PE spectrum, see Figure . For the anharmonic treatment, trajectories from SWS-AT+MD modeling were used (see ESI for details). A conventional Franck-Condon computation would allow direct evaluation of the vibrational structure. However, this requires optimization of cationic excited states, which can be considerably complicated due to their strong multireference character, as in the case of benzene. Alternatively, WS and SWS can be used as the fast and simple methods for estimation of line shapes, as we demonstrate in Figure . The spectra computed on the basis of MD are slightly red-shifted in the first three bands with respect to the WS-based values. This is probably due to anharmonicity.