Combining transition state theory with quasiclassical trajectory calculations. III. Applications to the three-dimensional H + H 2(ν) reaction

Abstract

A new method is described of using quasiclassical trajectories to study the dynamics of elementary reactions in three dimensions. Trajectories are initiated in the phase space of suitably chosen transition state and run forwards and backwards in time from the same starting point to simulate a complete collision. The transition state for a given vibrational level ν is determined by first finding pods (periodic orbiting dividing surfaces) on fixed-angle potential energy surfaces for which the action over one cycle of the pods motion is (ν + 1 2 ) h. The complete transition is then defined by joining these pods together. Methods are described for pseudo-randomly sampling the phase space of these transition states. Results for collisions of H + H 2(ν) with ν = 0–5 and 9 on the accurate Liu-Siegbahn-Truhlar-Horowitz surface are presented and compared with the results of conventional quasiclassical trajectory studies that have already been reported in the literature. Absolute values of rate constants are obtained using the adiabatic reactive sudden version of the transition state theory. Comparisons of our combined method with conventional techniques are encouraging and there is a considerable saving in computer time resulting from the elimination of trajectories which do not reach the strong interaction zone. Only slight differences are found when the energy of the transition state bending motion is set equal to its zero-point quantum value rather than selected from a classical Boltzmann distribution.