Xe+ Formation Following Photolysis Of Au-Xe: A Velocity Map Imaging Study

The photodissociation dynamics of Au-Xe leading to Xe+ formation via the Xi(1/2)-X-2 Sigma(+) (v`, 0) band system (41 500-41 800 cm(-1)) have been investigated by velocity map imaging. Five product channels have been indentified, which can be assigned to photoinduced charge transfer followed by photodissociation in either the neutral or the [Au-Xe](+) species. For the neutral species, charge transfer occurs via a superexcited Rydberg state prior to dissociative ionization, while single-photon excitation of the gold atom in Au+-Xe accesses an (Au+)*-Xe excited state that couples to a dissociative continuum in Au-Xe+. Mechanisms by which charge transfer occurs are proposed, and branching ratios for Xe+ formation via the superexcited Rydberg state are reported. The bond dissociation energy for the first excited state of Au+-Xe is determined to be similar to 9720 +/- 110 cm(-1). (c) 2011 American Institute of Physics. [doi:10.1063/1.3556944]