Time-resolved vacuum-ultraviolet photoelectron spectroscopy of the Ã1Au state of acetylene

Ultrafast time-resolved photoelectron spectra are reported for the vacuum-ultraviolet (VUV) photoionization of acetylene following excitation to the 1Au state via UV absorption at 200 nm. The excitation energy lies above the lowest dissociation threshold to C2H 2Σ+ + H, as well as above the threshold for adiabatic dissociation of the 1Au state to form C2H (⁠ 2Π) + H. The time-dependent mass spectra and photoelectron spectra provide insight into the intramolecular decay processes of the 1Au state. In addition, photoelectron spectra of the 1Au state with VUV light access both the 2Πu and 2Σg+ states of the ion, as well as the predicted, but previously unobserved, 1 2Πg state, which corresponds to a two-hole, one-particle configuration that lies in close proximity to the 2Σg+ state. The 1 2Πg state is split into 2A2 + 2B2 and 2Ag + 2Bg states in the cis and trans configurations, respectively. Electronic structure calculations, along with trajectory calculations, reproduce the principal features of the experimental data and confirm the assignment of the 1 2Πg state.