Solvation effects on chemical reaction dynamics in clusters: Photodissociation of HI inXeNHI

The photodissociation of HI in clusters of the type ${\mathrm{Xe}}_{\mathit{N}}$HI is studied theoretically to explore the possible occurrence and dynamics of the cage effect in small clusters (from N=1 to 12). The method used describes the H atom quantum mechanically, the heavy atoms classically. It is found that a cage effect, corresponding to transient vibrations of the H between heavy atoms, exists for all clusters, including XeHI. For N5 the resonances are long lived and dominate the process. Steric and structural factors cause this behavior.