### Abstract

The HF vibrational frequency shifts for Ar_{n}HF van der Waals (vdW) clusters with n=4-14 are predicted to be strongly isomer-specific, providing distinct spectroscopic signatures for different cluster isomers. This represents an extension of our recent studies of the size dependence of the vibrational frequency shift for Ar_{n}HF clusters [J. Chem. Phys. 101, 6359, 10 181 (1994)]. The HF vibrational frequency shifts calculated for the two or three lowest-energy isomers of each cluster size considered differ by at least a couple of wave numbers. Their relative magnitudes directly reflect the number of Ar atoms that each Ar_{n}HF isomer has in the first solvation shell around HF. The calculations are performed on pairwise additive intermolecular potential energy surfaces constructed from spectroscopically accurate Ar-Ar and anisotropic Ar-HF potentials. In the frequency shift calculations, the Ar_{n} subunit is treated as rigid, frozen in the geometry of one of the global or local Ar_{n}HF minima found previously by simulated annealing [J. Chem. Phys. 100, 7166 (1994)]. The 5D coupled intermolecular vibrational levels of what is now effectively a floppy Ar _{n}-HF dimer, are calculated highly accurately by the quantum 5D bound state methodology which is described in detail. The 5D vdW vibrational zero-point energy of the Ar_{n}HF cluster affects significantly the energy gap between various isomers.

Original language | English (US) |
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Pages (from-to) | 1829-1841 |

Number of pages | 13 |

Journal | The Journal of Chemical Physics |

Volume | 103 |

Issue number | 5 |

DOIs | |

State | Published - Jan 1 1995 |

### ASJC Scopus subject areas

- Physics and Astronomy(all)
- Physical and Theoretical Chemistry

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## Cite this

_{n}HF (n=4-14) van der Waals clusters: Quantum five-dimensional bound state calculations.

*The Journal of Chemical Physics*,

*103*(5), 1829-1841. https://doi.org/10.1063/1.469757