Bottlenecks isomerization theory

MRRKM theory, from RIT, from direct trajectory simulations, and, for reference purposes, from the RRKM theory. In particular, a test of the effect of the RRKM choice of transition state on the predicted rate of isomerization is made by neglecting the contribution of intramolecular energy transfer (Model No. 1). It is seen that the RRKM choice of transition state leads to considerable error the isomerization rate constant predicted is greater than those from the MRRKM theory and RIT by as much as a factor of 4. With intramolecular bottlenecks taken into account, both RIT and the MRRKM theory agree well with trajectory calculations. 

S. K. Gray and S. A. Rice, /. Chem. Phys., 86, 2020 (1987). Phase Space Bottlenecks and Statistical Theories of Isomerization Reactions. 

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