Effects of reagent rotation on the dynamics of the H2+OH reaction: A full dimension quantum study

Abstract

We have extended the time-dependent wave packet method to calculate cross sections and rate constants for rotationally excited initial states by using the centrifugal sudden (CS) approximation. A detailed study of the effects of rotational excitation of reagents on the title reaction on the WDSE PES has been carried out. It is found that (a) OH rotational excitation very mildly enhances the total cross section, (b) H2 rotational excitation quite substantially reduce the cross section, and (c) simultaneous OH and H2 rotational excitation has a largely uncorrelated effect. As a result, we found that the thermal rate constant can be obtained fairly accurately by only taking into account the effect of H2 rotation. A model calculation by changing the mass of an O atom reveals that the weak dependence of the cross section on OH rotation is not because the O atom is left relatively stationary by OH rotation. We speculate that it may be a general feature for the diatom-diatom reaction that the nonreactive diatom acts as a spectator not only vibrationally but also rotationally. It was also found that the “J-shifting” approximation works quite well for the reaction. On the other hand, the effect of K on the dynamics is found to be much stronger and more complicated than the J effect, making the “K-shifting” approximation not good for the reaction.