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ArnHF van der Waals clusters revisited : II. Energetics and HF vibrational frequency shifts from diffusion Monte Carlo calculations on additive and nonadditive potential-energy surfaces for n=1-12.

Jiang, H. and Xu, M. Z. and Hutson, J. M. and Bačić, Z. (2005) 'ArnHF van der Waals clusters revisited : II. Energetics and HF vibrational frequency shifts from diffusion Monte Carlo calculations on additive and nonadditive potential-energy surfaces for n=1-12.', Journal of chemical physics., 123 (5). 054305.

Abstract

The ground-state energies and HF vibrational frequency shifts of ArnHF clusters have been calculated on the nonadditive potential-energysurfaces (PESs) for n=2-7 and on the pairwise-additive PESs for the clusters with n=1-12, using the diffusionMonte Carlo (DMC) method. For n>3, the calculations have been performed for the lowest-energy isomer and several higher-lying isomers which are the closest in energy. They provide information about the isomer dependence of the HF redshift, and enable direct comparison with the experimental data recently obtained in helium nanodroplets. The agreement between theory and experiment is excellent, in particular, for the nonadditive DMC redshifts. The relative, incremental redshifts are reproduced accurately even at the lower level of theory, i.e., the DMC and quantum five-dimensional (rigid Arn) calculations on the pairwise-additive PESs. The nonadditive interactions make a significant contribution to the frequency shift, on the order of 10%–12%, and have to be included in the PESs in order for the theory to yield accurate magnitude of the HF redshift. The energy gaps between the DMC ground states of the cluster isomers are very different from the energy separation of their respective minima on the PES, due to the considerable variations in the intermolecular zero-point energy of different ArnHF isomers.

Item Type:Article
Additional Information:ISI:000231168700021
Full text:(VoR) Version of Record
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Status:Peer-reviewed
Publisher Web site:http://dx.doi.org/10.1063/1.1991856
Publisher statement:© 2005 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in The Journal of Chemical Physics 123, 054305 (2005) and may be found at http://dx.doi.org/10.1063/1.1991856
Date accepted:09 June 2005
Date deposited:19 August 2015
Date of first online publication:August 2005
Date first made open access:No date available

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