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Dynamics for CH/sub 3/F and CD/sub 3/F isolated in rare gas solids

Journal Article · · J. Chem. Phys.; (United States)
OSTI ID:5624436

High resolution infrared spectra have been obtained for CH/sub 3/F and CD/sub 3/F in argon and krypton matrices from 3 to 39 K. Low-temperature spectra show structure indicative of two stable monomer sites. As temperature is raised, the structure collapses to give symmetric peaks for each mode. The line shapes and their broadening with temperature show large dependence on the modes, isotope, and host matrix. On the basis of the absence of rovibrational structure and the very different line shapes for the various modes, we conclude that free or hindered rotation does not contribute to the absorption lines of methyl fluoride in argon or krypton matrices below 40 K. The mode dependent line broadening with increasing temperatures has been attributed to vibrational dephasing involving low energy site local phonon modes. Implications with regard to vibrational energy relaxation, which is currently thought to be dominated by a vibration to rotation energy transfer, are discussed.

Research Organization:
Los Alamos National Laboratory, University of California, Los Alamos, New Mexico 87545
OSTI ID:
5624436
Journal Information:
J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 76:4; ISSN JCPSA
Country of Publication:
United States
Language:
English