Quantum Dynamics of HF Photodissociation in Icosahedral Ar12HF Clusters: Rotational Control of the Hydrogen Atom Cage Exit

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Rotational wavefunctions of the HF molecule in an icosahedral Ar HF cluster electronic ground state

Burkhard Schmidt

The photodissociation dynamics of HF molecules embedded in icosahedral Ar12HF cluster 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.

Chem. Phys. Lett. 301 (3-4), 207-216 (1999)
DOI:10.1016/S0009-2614(99)00030-5

Movies available

Photodissociation of Molecules in Cluster

The movie shows the quantum wavepacket dynamics of photodissociation of HF molecule embedded in the first octahedral solvation shell comprising 12 Ar atoms upon sudden excitation from the electronic ground state (1 Σ) to the lowest dissociative state (1 Π). The corresponding quantum-dynamical hydrogen density dynamics exhibits strong quantum features, in particular bifurcations and interferences when the wavepacket is scattered between the rare gas atoms in the surrounding cluster.

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Acknowlewdgments

Courtesy by Visualization department of ZIB

Using Amira software