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Photodissociation of van der Waals Molecules -- Do Angular Momentum Constraints Determine Decay Rates?

Casassa, M. P. and Western, Colin M. and Janda, Kenneth C. (1984) Photodissociation of van der Waals Molecules -- Do Angular Momentum Constraints Determine Decay Rates? In: Resonances. ACS Symposium Series. No.263. American Chemical Society , Washington, DC, pp. 305-319. ISBN 9780841208650.

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Experimental data pertinent to the vibrational predissociation mechanism of two types of van der Waals complex are presented and discussed. First, variations in the infrared band shape for excitation of the ethylene out-of-plane wag, ν_7, in the series of molecules (C_2H_4)_2, C_2H_4:HF, C_2H_4:Ne are discussed in terms of structure and relaxation mechanisms. Second, rotationally resolved laser excited fluorescence spectra for NeBr_2 and NeCl_2 are presented. There is a strong dependence of decay rate on molecular structure. Relaxation lifetimes vary from less than 10^(-12) s for C_2H_4 dimer to greater than 10^(-5) s for NeCl_2. Trends observed are qualitatively predicted by consideration of linear and angular momentum gap arguments. Other possible interpretations are discussed.

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Additional Information:© 1984 American Chemical Society. Received June 11, 1984. Published in print 28 September 1984. The infrared spectroscopy of ethylene complexes was supported by the United States Department of Energy. The visible laser excited fluorescence work was supported by the National Science Foundation. The data for Figures 3 and 4 were obtained by Fritz Thommen and Dwight Evard using a single frequency laser borrowed from the San Francisco Laser Center supported by the National Science Foundation under Grant No. CHE79-16250. Kenneth C. Janda would like to acknowledge fellowships from the Alfred P. Sloan Foundation and the Camille and Henry Dreyfus Foundation. This is contribution no. 7029 from the Arthur Amos Noyes laboratory of Chemical Physics.
Funding AgencyGrant Number
Department of Energy (DOE)UNSPECIFIED
Alfred P. Sloan FoundationUNSPECIFIED
Camille and Henry Dreyfus FoundationUNSPECIFIED
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Arthur Amos Noyes Laboratory of Chemical Physics7029
Series Name:ACS Symposium Series
Issue or Number:263
Record Number:CaltechAUTHORS:20180404-152225008
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Official Citation:Photodissociation of van der Waals Molecules M. P. CASASSA, COLIN M. WESTERN, and KENNETH C. JANDA Resonances. September 28, 1984 , 305-319 DOI:10.1021/bk-1984-0263.ch016
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:85617
Deposited By: Ruth Sustaita
Deposited On:04 Apr 2018 22:40
Last Modified:15 Nov 2021 20:30

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