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Vibronic dephasing of anharmonic molecules. I. Theory and its application to the separability of intra- and intermolecular processes

Diestler, D. J. and Zewail, A. H. (1979) Vibronic dephasing of anharmonic molecules. I. Theory and its application to the separability of intra- and intermolecular processes. Journal of Chemical Physics, 71 (7). pp. 3103-3112. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:20120725-113704560

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Abstract

A quantum‐mechanical theory of vibronic dephasing of impurity molecules in condensed media is presented. An expression for the dephasing time is derived that exhibits explicit dependences upon microscopic properties of both impurity and medium. The expression, which contains the temperature dependence and the cross section for dephasing, is used to predict qualitatively and semiquantitatively some features of vibronic spectral lines in solids. Of particular interest are systems in which the influence of intramolecular properties (of the impurity) upon dephasing is separable from that of intermolecular properties (of the medium). The distinction between vibrational and purely electronic effects on vibronic dephasing is also emphasized.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1063/1.438717 DOIUNSPECIFIED
http://jcp.aip.org/resource/1/jcpsa6/v71/i7/p3103_s1PublisherUNSPECIFIED
Additional Information:© 1979 American Institute of Physics. Received 21 December 1978; accepted 28 June 1979. Online Publication Date: 25 July 2008. We are grateful to the National Science Foundation for support of the work reported here. We are also indebted to Professor David W. Oxtoby for helpful criticism and suggestions. Contribution No. 5945.
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Funding AgencyGrant Number
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Subject Keywords: VIBRATIONAL STATES, ELECTRONIC STRUCTURE, TEMPERATURE DEPENDENCE, SOLIDS, MOLECULAR CRYSTALS, SPECTRA
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Other Numbering System NameOther Numbering System ID
Caltech Arthur Amos Noyes Laboratory of Chemical Physics 5945
Classification Code:PACS: 78.40.-q, 33.20.Kf
Record Number:CaltechAUTHORS:20120725-113704560
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20120725-113704560
Official Citation: Vibronic dephasing of anharmonic molecules. I. Theory and its application to the separability of intra‐ and intermolecular processes D. J. Diestler and A. H. Zewail J. Chem. Phys. 71, 3103 (1979); http://dx.doi.org/10.1063/1.438717 (10 pages)
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:32714
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:25 Jul 2012 20:09
Last Modified:26 Dec 2012 15:44

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