TY - JOUR
T1 - Photodissociation of HF in ArnHF (n=1-14,54) van der Waals clusters
T2 - Effects of the solvent cluster size on the solute fragmentation dynamics
AU - Schröder, Thomas
AU - Schinke, Reinhard
AU - Liu, Suyan
AU - Bačić, Zlatko
AU - Moskowitz, Jules W.
PY - 1995
Y1 - 1995
N2 - A comprehensive study of the photodissociation of HF in ArnHF van der Waals clusters, with n=1-14,54, for an ultrashort δ(t)-pulse excitation, is presented. The emphasis is on the dependence of the photodissociation dynamics of the HF solute molecule on the size and geometry of the Arn solvent cluster. This cluster size range encompasses formation and closing of the first solvation shell, which occurs for n=12, the addition of the complete second solvent layer (n=54), as well as the change of the HF location in the cluster, from a surface site for n≤8 to the interior of a cage for n≥9 clusters. Evolution of the fragmentation dynamics is revealed by following how the H-atom kinetic energy and angular distributions, the survival probability, and cluster fragmentation patterns change as a function of the cluster size and structure. Classical trajectories are used to simulate the photodissociation dynamics. The probability distributions of the initial coordinates and momenta of the H and F atom are defined by accurate quantum five-dimensional eigenstates of the coupled, very anharmonic large amplitude intermolecular vibrations of HF in the cluster. All aspects of the dissociation process studied here are found to exhibit a strong dependence on the size and geometry of the ArnHF clusters.
AB - A comprehensive study of the photodissociation of HF in ArnHF van der Waals clusters, with n=1-14,54, for an ultrashort δ(t)-pulse excitation, is presented. The emphasis is on the dependence of the photodissociation dynamics of the HF solute molecule on the size and geometry of the Arn solvent cluster. This cluster size range encompasses formation and closing of the first solvation shell, which occurs for n=12, the addition of the complete second solvent layer (n=54), as well as the change of the HF location in the cluster, from a surface site for n≤8 to the interior of a cage for n≥9 clusters. Evolution of the fragmentation dynamics is revealed by following how the H-atom kinetic energy and angular distributions, the survival probability, and cluster fragmentation patterns change as a function of the cluster size and structure. Classical trajectories are used to simulate the photodissociation dynamics. The probability distributions of the initial coordinates and momenta of the H and F atom are defined by accurate quantum five-dimensional eigenstates of the coupled, very anharmonic large amplitude intermolecular vibrations of HF in the cluster. All aspects of the dissociation process studied here are found to exhibit a strong dependence on the size and geometry of the ArnHF clusters.
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U2 - 10.1063/1.470034
DO - 10.1063/1.470034
M3 - Article
AN - SCOPUS:36449009177
SN - 0021-9606
VL - 103
SP - 9228
EP - 9241
JO - The Journal of Chemical Physics
JF - The Journal of Chemical Physics
IS - 21
ER -