On non-RRKM unimolecular kinetics: Molecules in general, and CH3NC in particular
- 1 November 1973
- journal article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 59 (9), 4621-4632
- https://doi.org/10.1063/1.1680672
Abstract
Monte Carlo rate constants for model CH3NC isomerization, determined at 200, 100, and 70 kcal/mole, disagree with theoretical predictions. Also, three different approximate methods of generating initial conditions at 200 kcal lead to divergent results. The molecule does not appear to us to obey the random lifetime assumption of conventional unimolecular rate theory at any of these energies. A discussion is given of the systematics of this kind of effect, and comments are made on the relationship between our results and those obtained in the laboratory.Keywords
This publication has 26 references indexed in Scilit:
- RRKM Theory, the CH3NC Paradox, and the Decomposition of Hot-Atom Substitution ProductsThe Journal of Chemical Physics, 1972
- Vibrational spectra of 2,2-difluoropropaneSpectrochimica Acta Part A: Molecular Spectroscopy, 1971
- Unimolecular Decomposition and Intramolecular Energy Relaxation in the Suprahigh-Pressure RegionThe Journal of Chemical Physics, 1971
- Kinetic isotope effects in nonequilibrium thermal unimolecular systems. Ethyl isocyanide-d5The Journal of Physical Chemistry, 1969
- Thermal isomerization of isocyanides. Variation of molecular parameters. Ethyl isocyanideThe Journal of Physical Chemistry, 1969
- A valence force field for saturated hydrocarbonsSpectrochimica Acta, 1965
- The Thermal Unimolecular Isomerization of Methyl-d1 Isocyanide. Fall-Off and Inverse Isotope Effect1Journal of the American Chemical Society, 1965
- Vibrational analysis of the n-paraffins—IISpectrochimica Acta, 1963
- The Thermal Unimolecular Isomerization of Methyl Isocyanide. Fall-of BehaviourJournal of the American Chemical Society, 1962
- Force constants and normal co-ordinates of cyclopropane moleculesSpectrochimica Acta, 1960