Testing transition state theory on Kac-Zwanzig model (Q878342)

The authors numerically test the validity of the predictions of transition state theory (TST) and variational transition state theory (VTST) by applying the two theories to a variant of the Kac-Zwanzig model introduced by \textit{G. Ford, M. Kac} and \textit{P. Mazur} [J. Math. Phys. 6, 504--515 (1965; Zbl 0127.21605)] and \textit{R. Zwanzig} [J. Stat. Phys. 9, 215--220 (1973)] with a double-well potential. By exploiting the fact that in a suitable limit the model can be approximated by a two-state Markov chain, the exact transition rate constants are calculated and compared with the predictions of TST and VTST. Both theories give the exact average frequency of crossing a dividing surface in phase space that separates two metastable sets of interest, which leads to an overestimate of the actual rate constants since trajectories may cross the dividing surface many times in the course of each transition. VTST improves the results of TST in that it minimizes the rate of crossing among a given class of dividing surfaces. In the present case TST fails, while for an optimal dividing surface VTST gives the exact result. An assessment of the validity of the result is given in order to speculate on the reliability of VTST in more complex systems.