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Perturbation theory approach to dynamical tunneling splitting of local mode vibrational states in ABA molecules

Stuchebrukhov, A. A. and Marcus, R. A. (1993) Perturbation theory approach to dynamical tunneling splitting of local mode vibrational states in ABA molecules. Journal of Chemical Physics, 98 (11). pp. 8443-8450. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:STUjcp93b

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Abstract

We introduce a point of view for treating the dynamical tunneling splitting of symmetric local mode vibrational states in ABA molecules (A=H typically) which is the one we have employed in treating the vibrational spectroscopy of CH overtones in molecules such as (CX3)3YCCH. Namely, the vibrational coupling corresponding to the dynamical tunneling in semiclassical mechanics via many intermediate off-resonance weak transitions between initial and final states can be treated by a standard high-order perturbation theory. We apply that method to the present simpler problem of tunneling splittings in ABA molecules, and compare the results with those of exact diagonalization, the semiclassical method, and the periodic orbit quantization. Of all the approximate methods, the perturbation theory was found to provide the best approximation to the results of exact diagonalization for the system treated. The relationship between these three methods and application to the problem of vibrational relaxation in polyatomic molecules with tunneling mechanism of intramolecular vibrational relaxation is discussed.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1063/1.464502DOIUNSPECIFIED
http://link.aip.org/link/?JCPSA6/98/8443/1PublisherUNSPECIFIED
Additional Information:Copyright © 1993 American Institute of Physics. Received 18 December 1992; accepted 24 February 1993. The authors wish to thank Kevin Lehmann for many stimulating discussions as well as Jonathan Connor, Mark Child, and Eli Pollak for many useful comments on the subject of the present paper. We are pleased to acknowledge the financial support of the NSF. Arthur Amos Noyes Laboratory of Chemical Physics Contribution No. 8753.
Funders:
Funding AgencyGrant Number
National Science FoundationUNSPECIFIED
Subject Keywords:PERTURBATION THEORY, TUNNEL EFFECT, LINE SPLITTING, VIBRATIONAL STATES, HYDROCARBONS, METHYL COMPOUNDS, SILICON COMPOUNDS, POLYATOMIC MOLECULES
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Arthur Amos Noyes Laboratory of Chemical Physics8753
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Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:STUjcp93b
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ID Code:12355
Collection:CaltechAUTHORS
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Deposited On:13 Nov 2008 00:11
Last Modified:26 Dec 2012 10:30

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