X-ray spectroscopy at the carbon K-edge is highly sensitive to the changes in molecular structure and orbital occupancy, delivering accurate information about the energy of core and valence orbitals of molecules containing carbon atoms. The ability to laser-produce tabletop HHG sources reaching up to 300 eV opened opportunities to implement the laser pump-probe technique with ultraviolet (UV) excitation probed by soft x-ray radiation in the carbon K-edge region with tens of femtosecond time resolution. 1,2,3,4,5,6,7, Recently, we applied this technique to measure the x-ray spectrum of the benzene radical cation (Bz + ). Together with highlevel calculations using equation-of-motion coupled-cluster singles and doubles theory (EOM-CCSD), this study provided insight into the electronic structure of benzene (Bz) and its cation. Comparison of the x-ray absorption spectra of neutral Bz and of Bz + revealed a splitting of the two degenerate π* orbitals as well as an appearance of a new peak due to a new transition to the partially occupied π orbital resulting from the ionization. According to the calculations, the observed splitting in the cation spectrum was ascribed primarily to the spin coupling of the unpaired electron in the partially vacant π orbital with the unpaired electrons resulting from the excitation of one of the carbon 1s electrons to the vacant π* orbitals. 9,10 Jahn-Teller relaxation causing symmetry distortion was also considered.