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

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.