Product lambda-doublet ratios for the O(3P) + D2 reaction: A mechanistic imprint

TL;DR

This paper introduces a new method to calculate the ratio of Lambda-doublet states in the O(3P) + D2 reaction, explaining experimental preferences through stereodynamics and reaction mechanisms on multiple potential energy surfaces.

Contribution

The study develops a novel approach to predict Lambda-doublet ratios considering concurrent potential energy surfaces and stereodynamics, addressing discrepancies between theory and experiment.

Findings

The method accurately reproduces experimental Lambda-doublet populations.

Reaction on different potential energy surfaces exhibits distinct mechanistic pathways.

Propensity for the Pi(A') state arises from mechanistic differences on the PESs.

Abstract

In the last decade, the development of theoretical methods have allowed chemists to reproduce and explain almost all of the experimental data associated with elementary atom plus diatom collisions. However, there are still a few examples where theory cannot account yet for experimental results. This is the case for the preferential population of one of the $\Lambda$-doublet states produced by chemical reactions. In particular, recent measurements of the OD($^2\Pi$) product of the O($^3$P) + D$_2$ reaction have shown a clear preference for the $\Pi(A')$ $\Lambda$-doublet states, in apparent contradiction with {\em ab initio} calculations, which predict a larger reactivity on the $A"$ potential energy surface. Here we present a method to calculate the $\Lambda$-doublet ratio when concurrent potential energy surfaces participate in the reaction. It accounts for the experimental $\Lambda$-doublet populations via explicit consideration of the stereodynamics of the process. Furthermore, our results demonstrate that the propensity of the $\Pi(A')$ state is a consequence of the different mechanisms of the reaction on the two concurrent potential energy surfaces.