A test of the validity of the combined phase-space/trajectory method

Abstract

The validity of the combined phase−space/trajectory method of analysis of chemical reactions in thermal systems is tested by comparison of three−dimensional trajectory calculations for a reaction A + BB ? AB + B similar to the reaction F + H2 ? HF + H. Two sets of reactive trajectories at fixed total energy were generated using the combined method. For one, the dividing surface was located near the saddle point, in the entrance valley (4300 trials, 1001 reactive). For the other, the dividing surface was located around the corner in the exit channel (41702 trials, 244 reactive). Comparison of the two sets of reactive trajectories shows they are identical within statistical error and suggests the results are independent of the dividing surface location, as required for the method to be rigorously valid.