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Uniform semiclassical theory of avoided crossings

Uzer, T. and Noid, D. W. and Marcus, R. A. (1983) Uniform semiclassical theory of avoided crossings. Journal of Chemical Physics, 79 (9). pp. 4412-4425. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:20120712-144920694

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Abstract

A voided crossings influence spectra and intramolecular redistribution of energy. A semiclassical theory of these avoided crossings shows that when primitive semiclassical eigenvalues are plotted vs a parameter in the Hamiltonian they cross instead of avoiding each other. The trajectories for each are connected by a classically forbidden path. To obtain the avoided crossing behavior, a uniform semiclassical theory of avoided crossings is presented in this article for the case where that behavior is generated by a classical resonance. A low order perturbation theory expression is used as the basis for a functional form for the treatment. The parameters in the expression are evaluated from canonical invariants (phase integrals) obtained from classical trajectory data. The results are compared with quantum mechanical results for the splitting, and reasonable agreement is obtained. Other advantages of the uniform method are described.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1063/1.446326DOIUNSPECIFIED
http://jcp.aip.org/resource/1/jcpsa6/v79/i9/p4412_s1PublisherUNSPECIFIED
Additional Information:© 1983 American Institute of Physics. Received 25 May 1983; accepted 23 July 1983. We are pleased to acknowledge the support of the present research by the U.S. Department of Energy under contract W -7405-eng-26 with the Union Carbide Corporation (at Oak Ridge) and by a grant from the National Science Foundation (at the California Institute of Technology). We thank Dr. J. N. L. Connor for his helpful comments.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)W-7405-eng-26
Union Carbide CorporationUNSPECIFIED
NSFUNSPECIFIED
Subject Keywords:polarizability; dimers; van der waals forces; helium; hydrogen; neon; nitrogen; hartree−fock method
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Caltech Arthur Amos Noyes Laboratory of Chemical Physics6837
Classification Code:PACS: 31.15.A-; 33.15.Kr; 34.20.-b
Record Number:CaltechAUTHORS:20120712-144920694
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20120712-144920694
Official Citation:Uniform semiclassical theory of avoided crossings T. Uzer, D. W. Noid, and R. A. Marcus, J. Chem. Phys. 79, 4412 (1983), DOI:10.1063/1.446326
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:32396
Collection:CaltechAUTHORS
Deposited By: Aucoeur Ngo
Deposited On:12 Jul 2012 23:16
Last Modified:26 Dec 2012 15:31

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