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note
-
While it is tempting to equate the reciprocal of our τ values to the corresponding unimolecular rate constants for HT, it is strictly incorrect to do so because the trajectories are halted immediately following HT, without allowing them the opportunity to recross from product well into reactant well. That is, we are assuming infinitely fast deactivation in the product well, whereas dissipation in the reactant well occurs only through dynamics of the atoms. The reciprocal of our τ values would be equal to the unimolecular rate constant in the high-pressure limit (i.e. in solution) if intramolecular vibrational energy redistribution were very much faster than passage over the reaction barrier, but we have no information about that. We are grateful to a referee and to Professor D. G. Truhlar for helpful comments on this point.
-
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67
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84920350628
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note
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F-tests performed to compare the relative qualities of the monoexponential and biexponential fits to the decay data for 4b revealed that the biexponential fit is in fact significantly better at the 95% confidence limit.
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note
-
Although the decay data for 4b are expressed more precisely by a biexponential function, the kinetic isotope effect for HT between 4a and 4b is calculated by using the rate constant obtained from the monoexponential fit to the decay data for 4b. Errors introduced by using this fit are assumed to be small.
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