Conformational kinetics of methyl nitrite. I. NMR spectral evidence for statistical intramolecular vibrational redistribution

Article abstract of DOI:10.1063/1.446895

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 β_p for CO2 of 0.95(8) for activation of syn-anti conformational exchange at 258.8 K.

Full text of DOI:10.1063/1.446895

Conformational kinetics of methyl nitrite. I. NMR spectral evidence for statistical
intramolecular vibrational redistribution
J. Paul Chauvel Jr., Claire B. Conboy, Wilbert M. Chew, Gerald B. Matson, Cheryl A. Spring, Brian D. Ross, and
Nancy S. True
Citation: The Journal of Chemical Physics 80, 1469 (1984); doi: 10.1063/1.446895
View online: http://dx.doi.org/10.1063/1.446895
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/80/4?ver=pdfcov
Published by the AIP Publishing
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
30.160.4.77 On: Sat, 20 Dec 2014 04:13:16
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
30.160.4.77 On: Sat, 20 Dec 2014 04:13:16
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
30.160.4.77 On: Sat, 20 Dec 2014 04:13:16
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP: 130.160.4.77
On: Sat, 20 Dec 2014 04:13:16

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
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