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

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 122; no. 10; pp. 2739 - 2750
• Main Authors: Jambrina, Pablo G, Menéndez, M, Zanchet, A, García, E, Aoiz, F. J
• Format: Journal Article
• Language: English
• Published: American Chemical Society 15.03.2018
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.7b11826

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.