Constraints at the transition state of the D + H2 reaction: Quantum bottlenecks vs. stereodynamics

Abstract

This article presents a quasiclassical trajectory method for the calculation of cumulative reaction probabilities by sampling of the helicity quantum number of the reagents (k). The method is applied to the D + H 2 reaction at various total angular momentum (J) values, and the helicity-resolved quasiclassical cumulative reaction probabilities are compared to their quantum mechanical counterparts. The agreement between the two sets of results is fairly good. In particular, k-dependent, J-independent reaction thresholds found with quantum methods are reproduced by the quasiclassical calculations. The shift of these thresholds with increasing k, which has been previously attributed to the quantum bottleneck states taking part in the reaction, is revisited and discussed also in terms of the reaction stereodynamics. © Royal Society of Chemistry