Casassa, Michael P. and Bomse, David S. and Beauchamp, J. L. and Janda, Kenneth C. (1980) Infrared photochemistry of ethylene clusters. Journal of Chemical Physics, 72 (12). pp. 6805-6806. ISSN 0021-9606 http://resolver.caltech.edu/CaltechAUTHORS:CASjcp80
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Infrared irradiation of ethylene clusters formed in supersonic molecular beams, using a low power cw CO2 laser, results in the photodissociation of a large fraction of the van der Waals molecules. Under such conditions, infrared absorption intensity exhibits first-order power dependence and is readily detected as loss in molecular beam intensity. Intramolecular energy transfer rates, determined by measuring spectral linewidths, are shown to vary with the vibrational mode initially excited. Ethylene clusters containing one quantum of vibrational energy corresponding to the nun7 fundamental in the monomer (949 cm^–1) have a vibrationally predissociative lifetime of 0.33 psec. In comparison, the relaxation rate of ethylene-d4 clusters with one quantum of excitation corresponding to the nu12 (1078 cm^–1) mode of C2D4 is 0.7 psec.
|Additional Information:||Copyright © 1980 American Institute of Physics. (Received 26 March 1980; accepted 15 April 1980) This work was supported by the Research Corporation and the Division of Chemical Sciences, Office of Basic Energy Sciences, U.S. Department of Energy under contract No. DE-AS03-76SF00767. Acknowledgment is made to the Donors of the Petroleum Research Fund, administered by the American Chemical Society, for partial support of this research. [M.P.C. was a] National Science Foundation Predoctoral Fellow. [D.S.B. was a]Josephine de Karman Fellow and Monsanto Fellow. Division of Chemistry and Chemical Engineering, Contribution number 6183.|
|Subject Keywords:||VIBRATIONAL STATES, RELAXATION, INFRARED RADIATION, LASER RADIATION, PHOTOCHEMICAL REACTIONS, ETHYLENE, MOLECULAR BEAMS, CROSS SECTIONS|
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|Deposited On:||11 Jun 2008|
|Last Modified:||26 Dec 2012 10:05|
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