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Large-amplitude quantum mechanics in polyatomic hydrides II A particle-on-a-sphere model for XHn (n=4,5).

Deskevich, Michael P. and Mccoy, Anne B. and Hutson, Jeremy M. and Nesbitt, David J. (2008) 'Large-amplitude quantum mechanics in polyatomic hydrides II A particle-on-a-sphere model for XHn (n=4,5).', Journal of chemical physics., 128 (9). 094306.

Abstract

This paper describes the application of a relatively simple, but computationally tractable, “particle-on-a-sphere” (POS) model for quantum-mechanical calculation of large-amplitude, H atom dynamics in polyatomic hydrides (XHn), based on radially relaxed, two-dimensional angular motion of H atoms on the surface of a sphere. This work focuses on systems with many degrees of freedom, i.e., XH4 (eight dimensional) and XH5 (ten dimensional), with corresponding molecular analogs of CH4 and CH5+ and is applicable to rovibrationally excited states with J ≥ 0. A pairwise-additive potential fit for CH5+, which yields remarkable agreement with geometries, energies, and barrier heights on the full-dimensional surface of Brown et al. [J. Chem. Phys. 121, 4105 (2004)] is presented. Comparisons with experimental data and diffusion quantum Monte Carlo (DMC) methods test convergence for the POS model and provide insight into multidimensional quantum rovibrational dynamics. In particular, POS energy-level patterns for a series of scaled CH5+ potentials indicate an absence of strong tunneling behavior, consistent with the highly delocalized wave functions, large zero-point energies, and small interconversion barriers noted in previous DMC studies of Brown et al.

Item Type:Article
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Status:Peer-reviewed
Publisher Web site:http://dx.doi.org/10.1063/1.2828478
Publisher statement:© 2018 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 Deskevich, Michael P. and Mccoy, Anne B. and Hutson, Jeremy M. and Nesbitt, David J. (2008) 'Large-amplitude quantum mechanics in polyatomic hydrides II A particle-on-a-sphere model for XHn (n=4,5).', Journal of chemical physics., 128 (9). 094306 and may be found at http://dx.doi.org/10.1063/1.2828478
Date accepted:No date available
Date deposited:17 April 2015
Date of first online publication:2008
Date first made open access:No date available

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