Slow photoelectron velocity-map imaging spectroscopy of the phenoxide and thiophenoxide anions

Abstract

High resolution anion photodetachment spectra of the phenoxide and thiophenoxide anions were obtained with slow electron velocity-map imaging. The spectra show transitions to the ²B₁ neutral states of both species and to the òB₂ state of the thiophenoxy radical. Comparison of the spectra with Franck-Condon simulations allows several gas-phase vibrations to be assigned. The adiabatic electron affinities are determined to be 2.2538(8) eV and 2.3542(6) eV for phenoxy and thiophenoxy, respectively. The term energy of the òB₂ state of thiophenoxy is found to be 0.3719(9) eV, higher than the values reported in photodissociation experiments of thiophenol.