Table-Top X-ray Spectroscopy of Benzene Radical Cation

Ultrafast table-top x-ray spectroscopy at the carbon K-edge is used to measure the x-ray spectral features of benzene radical cations (Bz⁺). The ground state of the cation is prepared selectively by two-photon ionization of neutral benzene, and the x-ray spectra are probed at early times after the ionization by transient absorption using x-rays produced by high harmonic generation (HHG). Bz⁺ is well known to undergo Jahn-Teller distortion, leading to a lower symmetry and splitting of the π orbitals. Comparison of the x-ray absorption spectra of the neutral and the cation reveals a splitting of the two degenerate π* orbitals as well as an appearance of a new peak due to excitation to the partially occupied π -subshell. The π* orbital splitting of the cation, elucidated on the basis of high-level calculations in a companion theoretical paper [Vidal et al, submitted to J. Phys. Chem. Lett.; ChemRxiv link: doi XXXXX], is discovered to be due to both the symmetry distortion and even more dominant spin coupling of the unpaired electron in the partially vacant π orbital (from ionization) with the unpaired electrons resulting from the transition from the 1s_C core orbital to the fully vacant π* orbitals.