Observation of the symmetry-forbidden 5sigmau-->ksigmau CS2 transition: a vibrationally driven photoionization resonance.
Vibrationally resolved photoelectron spectroscopy and Schwinger calculations are used to characterize a new resonance phenomenon in the 5sigma(u)-->ksigma(u) photoionization of CS2. This resonant channel is symmetry forbidden, yet is observable because it is activated by the antisymmetric stretching vibration. In addition, we show that a Franck-Condon breakdown occurs even though the energy dependence of the cross section is insensitive to geometry changes, which is unprecedented in photoionization.
Rathbone
G J
GJ
Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803, USA.
Poliakoff
E D
ED
Bozek
John D
JD
Lucchese
R R
RR