Λ-Doublet Propensities for Reactions on Competing A' and A″ Potential Energy Surfaces: O(3 P) + N2 and O(3 P) + HCl.

ABSTRACT

This work presents scattering calculations for the O(3 P) + N2(1Σ) → NO(2Π) + N(4S) and for the O(3 P) + HCl(1Σ) → OH(2Π) + Cl(2P) reactions with a focus on the prediction of the Λ-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 Λ-doublet populations through the explicit consideration of the stereodynamics of the reaction, we predict that the population of NO and OH on the two Λ-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 Π( A') and Π( A″) states, respectively.