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

The photodissociation of HI in clusters of the type XeNHI 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 N<5 these resonances are short lived and contribute little. For N>5 the resonances are long lived and dominate the process. Steric and structural factors cause this behavior.