Dissociative photoionization of acetaldehyde in the 10.2–19.5 eV VUV range

Abstract

The valence-shell dissociative photoionization of acetaldehyde has been investigated by means of the photoion photoelectron coincidence technique in conjunction with tuneable synchrotron radiation. The experimental results consist of threshold photoelectron spectra for the parent ion and for each fragment ion in the 10.2–19.5 eV photon energy range, along with (ion, e) kinetic energy coincidence diagrams obtained from measurements at fixed photon energies. The results are complemented by high-level ab initio calculations of potential energy curves as a function of the C–H bond distance. The nudged elastic band (NEB) method has been employed to connect the parent ion Franck–Condon region to the formation of the HCO⁺, CH₃⁺ and CH₄⁺ ion fragments. Appearance energies have been determined for six fragment ions with an improved accuracy, including two fragmentation channels, which to the best of our knowledge have not been reported previously, i.e. the formation of CH₂CO⁺, lying at 13.10 ± 0.05 eV, and the formation of CH₂⁺ at 15.1 ± 0.1 eV. Based on both experimental and theoretical results, the dissociation dynamics following ionization of acetaldehyde into the different fragmentation channels are discussed.