Theoretical Study of the Photochemical Mechanisms of the Electronic Quenching of NO(A2Σ+) with CH4, CH3OH, and CO2.

Abstract

The electronic quenching of NO(A2Σ+) with molecular partners occurs through complex non-adiabatic dynamics that occurs on multiple coupled potential energy surfaces. Moreover, the propensity for NO(A2Σ+) electronic quenching depends heavily on the strength and nature of the intermolecular interactions between NO(A2Σ+) and the molecular partner. In this paper, we explore the electronic quenching mechanisms of three systems: NO(A2Σ+) + CH4, NO(A2Σ+) + CH3OH, and NO(A2Σ+) + CO2. Using EOM-EA-CCSD calculations, we rationalize the very low electronic quenching cross-section of NO(A2Σ+) + CH4 as well as the outcomes observed in previous NO + CH4 photodissociation studies. Our analysis of NO(A2Σ+) + CH3OH suggests that it will undergo facile electronic quenching mediated by reducing the intermolecular distance and significantly stretching the O-H bond of CH3OH. For NO(A2Σ+) + CO2, intermolecular attractions lead to a series of low-energy ON-OCO conformations in which the CO2 is significantly bent. For both the NO(A2Σ+) + CH3OH and NO(A2Σ+) + CO2 systems, we see evidence of the harpoon mechanism and low-energy conical intersections between NO(A2Σ+) + M and NO(X2Π) + M. Overall, this work provides the first detailed theoretical study on the NO(A2Σ+) + M potential energy surface of each of these systems and will inform future velocity map imaging experiments.