VUV photoionization and dissociative photoionization of o-xylene: experimental and theoretical insights.

The photoionization and dissociative photoionization of o-xylene have been studied using synchrotron radiation vacuum ultraviolet light with the photon energy in the range of 8.0–13.0 eV. The ionization energy of o-xylene and the appearance energies for the main fragment ions C 8 H 9 + , C 7 H 7 + and C 6 H 6 + were determined to be 8.45, 11.08, 11.47 and 11.17 eV, respectively, with photoionization efficiency spectra (PIES). Three dissociation pathways of parent ions are investigated by experimental photoionization and the quantum-chemical calculations. The fragment ions C 7 H 7 + derived from parent ions involved hydrogen atom transfer rather than direct dissociation. Particularly, detailed mechanisms of dissociation C 6 H 6 + are presented for the first time in this work. In addition, the geometries of the intermediates (INTs), transition states (TSs) and products have been performed at B3LYP/6-311 + + G (d, p) level. The mechanisms of dissociative photoionization of o-xylene and the INTs and TSs involved are discussed in detail. [ABSTRACT FROM AUTHOR]