Dissociative double photoionization of benzene molecules in the 26–33 eV energy range

Abstract

A time-of-flight mass spectrometer with a position sensitive ion detector was used to study the dissociative double ionization of benzene by UV synchrotron radiation. The threshold energy for the main dissociative processes, leading to CH₃⁺ + C₅H₃⁺, C₂H₃⁺ + C₄H₃⁺ and C₂H₂⁺ + C₄H₄⁺ ion pairs were characterized by exploiting a photoelectron-photoion-photoion-coincidence technique, giving 27.8 ± 0.1, 29.5 ± 0.1, and 30.2 ± 0.1 eV, respectively. The first reaction also proceeds via the formation of a metastable C₆H₆²⁺ dication. The translational kinetic energy of the ionic products was evaluated by measuring the position of ions arriving to the detector. Theoretical calculations of the energy and structure of dissociation product ions were performed to provide further information on the dynamics of the charge separation reactions following the photoionization event.