Journal of Physical Chemistry A, Vol.109, No.7, 1400-1404, 2005
Recrossings and transition-state theory
When classical trajectory calculations are run on the two isomerization reactions NCCN reversible arrow NCNC and CH3-CN reversible arrow CH3NC over a long period of time, up to ca. 0.2 mus each, one finds many more recrossings than actual reactive events. In these calculations a "recrossing" is defined as passage over the potential barrier separating the two species followed by return to the original side within 0.2 ps. For the C2N2 case there are about twice as many crossings of the barrier as there are genuine reactive events, and for CH3CN, there are about 10 times as many. Long-term mean residence times, tau(CN)(infinity) and tau(NC)(infinity), in reactant and product wells are compared with the corresponding mean first passage times, tau(CN)(1) and tau(NC)(1), the latter found by terminating the trajectories at the first crossing of the barrier. For the NCCN reversible arrow NCNC reaction, except at the lowest energies, the mean residence times are exactly twice the mean first passage times, implying that the transition-state theory transmission coefficient, as traditionally defined, should be kappa = 0.5.