Rathbone G J, Poliakoff E D, Bozek John D, Lucchese R R
Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803, USA.
Phys Rev Lett. 2004 Apr 9;92(14):143002. doi: 10.1103/PhysRevLett.92.143002. Epub 2004 Apr 8.
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.
