### Abstract

A comprehensive study of the photodissociation of HF in Ar_{n}HF 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 Ar_{n} 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 Ar_{n}HF clusters.

Original language | English (US) |
---|---|

Pages (from-to) | 9228-9241 |

Number of pages | 14 |

Journal | The Journal of chemical physics |

Volume | 103 |

Issue number | 21 |

State | Published - 1995 |

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### ASJC Scopus subject areas

- Atomic and Molecular Physics, and Optics

### Cite this

*The Journal of chemical physics*,

*103*(21), 9228-9241.

**Photodissociation of HF in ArnHF (n=1-14,54) van der Waals clusters : Effects of the solvent cluster size on the solute fragmentation dynamics.** / Schröder, Thomas; Schinke, Reinhard; Liu, Suyan; Bacic, Zlatko; Moskowitz, Jules W.

Research output: Contribution to journal › Article

*The Journal of chemical physics*, vol. 103, no. 21, pp. 9228-9241.

}

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 - Bacic, 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.

UR - http://www.scopus.com/inward/record.url?scp=36449009177&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=36449009177&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:36449009177

VL - 103

SP - 9228

EP - 9241

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 21

ER -