Nonresonant (VV) transfer between molecules dissolved in liquid N2, liquid Ar, and liquid N2/Ar mixtures

In order to investigate the effect of the solvent on nonresonant (VV) processes, rate constants have been measured for the deactivation of N2(v=1) and CO(v=1) in liquid N2/Ar mixtures at 85 K. The systems studied are relaxation of 14N2, 12C16O, and 13C16O by both O2 and CH4. Measurements were taken...

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Bibliographic Details
Published in:The Journal of chemical physics 1995-03, Vol.102 (10), p.4093-4100
Main Authors: Wilson, G. J., Turnidge, M. L., Simpson, C. J. S. M.
Format: Article
Language:English
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Summary:In order to investigate the effect of the solvent on nonresonant (VV) processes, rate constants have been measured for the deactivation of N2(v=1) and CO(v=1) in liquid N2/Ar mixtures at 85 K. The systems studied are relaxation of 14N2, 12C16O, and 13C16O by both O2 and CH4. Measurements were taken in liquid Ar, liquid N2, and in solvent mixtures. The rate constants in liquid Ar solution equal those in the gas phase at the same temperature. The rate constants fall nonlinearly with the addition of N2 to the solvent. The decrease on changing the solvent from liquid Ar to liquid N2 is 30% for the deactivation of N2(v=1) and 10% for CO(v=1). These results would not be predicted by current formulations of the isolated binary collision (IBC) hypothesis and suggest that one or more N2 molecules in the shell of solvent molecule surrounding vibrationally excited N2 or CO perturb the energy transfer process.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.468537