Fully rotationally resolved ZEKE photoelectron spectroscopy of C6H6 and C6D6: photoionization dynamics and geometry of the benzene cation

A comprehensive set of spectra for the benzene cation and the perdeuterated benzene cation has been recorded with full rotational resolution using zero kinetic energy photoelectron spectroscopy (ZEKE) at high resolution (up to 0.2 cm^?1), using a slow-rising extraction pulse. With different rovibronic levels in the S₁ 6^l state as intermediate resonance, the rotational transitions to the vibronic ground state of the cation have been recorded using two-colour, two-photon resonance enhanced multiphoton ionization. A simple spectator model has been employed to simulate the intensities of the ZEKE transitions. By fitting the simulations to the recorded spectra, improved values for the rotational constants and the Coriolis coupling parameters of benzene and perdeuterated benzene have been obtained. The CC and CH bond lengths of the cation have been deduced. The spectator model is shown to be reliable despite the fact that no specific allowance is made for the effect of final state interactions on the signal intensity.