Isomer dependence of HF vibrational frequency shift for ArnHF (n=4-14) van der Waals clusters

Quantum five-dimensional bound state calculations

Suyan Liu, Zlatko Bacic, Jules W. Moskowitz, Kevin E. Schmidt

Research output: Contribution to journalArticle

Abstract

The HF vibrational frequency shifts for ArnHF 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 ArnHF 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 ArnHF 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 Arn subunit is treated as rigid, frozen in the geometry of one of the global or local ArnHF 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 ArnHF cluster affects significantly the energy gap between various isomers.

Original languageEnglish (US)
Pages (from-to)1829-1841
Number of pages13
JournalThe Journal of chemical physics
Volume103
Issue number5
StatePublished - 1995

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Vibrational spectra
Isomers
frequency shift
isomers
Shells (structures)
Potential energy surfaces
zero point energy
Solvation
simulated annealing
Simulated annealing
Dimers
solvation
Energy gap
potential energy
dimers
signatures
methodology
Atoms
Geometry
geometry

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Isomer dependence of HF vibrational frequency shift for ArnHF (n=4-14) van der Waals clusters : Quantum five-dimensional bound state calculations. / Liu, Suyan; Bacic, Zlatko; Moskowitz, Jules W.; Schmidt, Kevin E.

In: The Journal of chemical physics, Vol. 103, No. 5, 1995, p. 1829-1841.

Research output: Contribution to journalArticle

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