Quantum dynamics of HF photodissociation in icosahedral Ar12HF clusters:: rotational control of the hydrogen atom cage exit

The photodissociation dynamics of HF molecules embedded in icosahedral HFAr12 clusters upon excitation with an ultrashort light-pulse is investigated. Assuming a frozen cluster, three-dimensional symmetry adapted wavepackets for the hydrogen photofragment are propagated in time. The emphasis is on the dependence of the HF photodissociation dynamics on the initial quantum state of the diatomic molecule. Depending on the spatial characteristics of the initial rotational state inside the rare gas cage, different cage exit probabilities are found. This opens the way to a rotational control of photochemistry of small molecules in weakly bound clusters. (C) 1999 Elsevier Science B.V. All rights reserved.