Λ-Doublet Propensities for Reactions on Competing A′ and A" Potential Energy Surfaces: O(3P) + N2 and O(3P) plus HCl

This work presents scattering calculations for the O(P-3) + N-2((1)Sigma) -> NO((2)Pi) + N(S-4) and for the O(P-3) + HCl((1)Sigma) -> OH((2)Pi) + Cl(P-2) reactions with a focus on the prediction of the Lambda-doublet populations in which NO and OH are produced. Both reactions can take place on two competing potential energy surfaces of symmetries (3)A' and (3)A '' that correlate reagents with products but with very distinct topographies. As a result, they exhibit very different dynamical behaviors and total reactivity. Using a method that relates the reaction yield on the two competing surfaces to the Lambda-doublet populations through the explicit consideration of the stereodynamics of the reaction, we predict that the population of NO and OH on the two Lambda-doublet sates is surprisingly similar for both systems. These results contradict the model that assumes that collisions on the (3)A' and (3)A '' would give rise to products in the Pi(A') and Pi(A '') states, respectively.