Journal of Chemical Physics p. 1469 - 1476 (1984)
Update date:2022-08-17
Topics:
Chauvel, J. Paul
Conboy, Claire B.
Chew, Wilbert M.
Matson, Gerald B.
Spring, Cheryl A.
et al.
Pressure dependent rate constants for syn <*> anti conformational exchange in gaseous methyl nitrite and in gaseous methyl nitrite-CO2 mixtures have been obtained from line shape analyses of 1H NMR spectra.The pressure dependence of the exchange rates is consistent with a specific reaction rate constant of ca. 1*109/s which agrees with RRKM calculations demonstrating that intramolecular vibrational redistribution is occurring at the statistical limit in methyl nitrite molecules with ca. 12 kcal/mol of internal vibrational energy.At 12 kcal/mol methyl nitrite has a state density of ca. 160/cm-1.These results indicate strong anharmonic and /or Coriolis coupling between vibrational levels.Bimolecular rate data for methyl nitrite and methyl nitrite-CO2 mixtures are consistent with a collisional efficiency βp for CO2 of 0.95(8) for activation of syn-anti conformational exchange at 258.8 K.
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