Time-Resolved Dynamics of Thermal Isomerization in Cesium-Halide Cluster Anions

We have performed time-resolved studies of the dynamics of thermal isomerization occurring in certain cesium-halide cluster anions. Using a pump-probe technique, we have observed the repopulation of a photodepleted isomer within an ensemble as a function of time by monitoring the photoelectron spectrum. The rates of isomerization increase and the isomer lifetimes decrease as functions of temperature. The clusters undergo a gradual phase transition from solid-like to liquid-like states with liquid-like behavior obtained at approximately 500 K, much lower than the bulk melting temperatures of approximately 900 K.