An unusual π* shape resonance in the near-threshold photoionization of S₁ para-difluorobenzene

Previously reported dramatic changes in photoelectron angular distributions (PADs) as a function of photoelectron kinetic energy following the ionization of S₁p-difluorobenzene are shown to be explained by a shape resonance in the b₂g symmetry continuum. The characteristics of this resonance are clearly demonstrated by a theoretical multiple-scattering treatment of the photoionization dynamics. New experimental data are presented which demonstrate an apparent insensitivity of the PADs to both vibrational motion and prepared molecular alignment, however, the calculations suggest that strong alignment effects may nevertheless be recognized in the detail of the comparison with experimental data. The apparent, but unexpected, indifference to vibrational excitation is rationalized by considering the nature of the resonance. The correlation of this shape resonance in the continuum with a virtual π* antibonding orbital is considered. Because this orbital is characteristic of the benzene ring, the existence of similar resonances in related substituted benzenes is discussed.K.L.R. acknowledges EPSRC for funding Grant Nos. GR/M83759 and GR/R72297, including postdoctoral support for J.A.D. and S.M.B