Equilibrium structures and approximate HF vibrational red shifts for ArnHF (n=1-14) van der Waals clusters

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

Research output: Contribution to journalArticle

Abstract

This paper presents a theoretical study of the size evolution of equilibrium structures and approximate HF vibrational red shifts for Ar nHF van der Waals clusters, with n = 1-14. Pairwise additive Ar nHF intermolecular potential energy surfaces were constructed from spectroscopically accurate Ar-Ar and anisotropic Ar-HF potentials. The latter depend on vibrational excitation of the HF monomer. The global and energetically close-lying local minima of ArnHF, n = 1-14, for HF v=0 and v=1, were determined using simulated annealing followed by a direct minimization scheme. For ArnHF clusters with n≤8, the lowest-energy structure always has HF bound to the surface of the Arn subunit. In contrast, for n≥9, the global minimum of ArnHF corresponds to HF inside a cage. Ar12HF has the minimum-energy configuration of an HF-centered icosahedron, which appears to be unusually stable. Size dependence of the HF vibrational red shift in ArnHF (n=1-14) clusters was investigated by means of a simple approximation, where the red shift was represented by the energy difference between the global minima of a cluster obtained for HF v=0 and v=1, respectively. The approximation reproduced rather accurately the experimentally determined variation of the ArnHF red shift with the number of Ar atoms, for n=1-4, although it overestimated their magnitude. For larger ArnHF clusters, 4<n≤14, a nonmonotonic, step-like dependence of the red shift on the cluster size is predicted, which can be interpreted in terms of changes in the minimum-energy cluster geometries. The predicted red shift for the icosahedral Ar12HF, where the first solvation shell is full, is 44.70 cm-1, which is only 5.4% higher than the experimental HF vibrational red shift in an Ar matrix, of 42.4 cm -1.

Original languageEnglish (US)
Pages (from-to)7166-7181
Number of pages16
JournalThe Journal of chemical physics
Volume100
Issue number10
StatePublished - 1994

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Potential energy surfaces
Solvation
Simulated annealing
red shift
Monomers
Atoms
Geometry
energy
simulated annealing
approximation
solvation
monomers
potential energy
optimization
matrices
geometry
configurations
excitation
atoms

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

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Equilibrium structures and approximate HF vibrational red shifts for ArnHF (n=1-14) van der Waals clusters. / Liu, Suyan; Bacic, Zlatko; Moskowitz, Jules W.; Schmidt, Kevin E.

In: The Journal of chemical physics, Vol. 100, No. 10, 1994, p. 7166-7181.

Research output: Contribution to journalArticle

Liu, Suyan ; Bacic, Zlatko ; Moskowitz, Jules W. ; Schmidt, Kevin E. / Equilibrium structures and approximate HF vibrational red shifts for ArnHF (n=1-14) van der Waals clusters. In: The Journal of chemical physics. 1994 ; Vol. 100, No. 10. pp. 7166-7181.
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