Molecular properties and excited state van der Waals potentials in the NO A²Σ⁺ + O₂ XΣ_g⁻ collision complex

Abstract

We characterize NO A2S+ + O2 X3S g Van der Waals (VdW) Potential Energy Surface (PES) with RHF/RCCSD(T) and CASSCF/CASPT2 calculations. To do this, we first assess our computational setup to...

Differential Cross Sections for Pair-Correlated Rotational Energy Transfer in NO(A2Σ+) + N2, CO, and O2: Signatures of Quenching Dynamics

“…These results are very surprising, particularly in light of the vdW PES that we recently published for NO(A) + O 2 . 47 This PES has an N-end minimum, depth −95 cm −1 , tightly focused around the linear ON−OO geometry, very similar to those also observed in the NO(A)-Ar PES. 50 This is fully consistent with the observed sharp forward scattering peak.…”

“…The observed scattering dynamics for collisions with N 2 , and to a lesser extent, CO, are explicable in terms of known details of the vdW PESs for the NO(A)-N 2 and NO(A)-CO systems. 46,47 The dynamics observed for collisions with O 2 are consistent with only high-impact-parameter glory scattering, while there is an absence of scattering arising from the lowerimpact parameter, repulsive wall collisions. Considering the literature NO(A) electronic quenching cross sections, and recent electronic structure calculations for all three systems, we interpret this as the result of quenching removing NO(A) that undergoes lower-impact-parameter collisions with O 2 .…”

“…In particular, very little rotational excitation is observed in either fragment for collisions with O 2 , for which the DCSs are also almost exclusively forward scattered. We discuss these results in the context of the substantially different electronic quenching kinetics of NO­(A) with the three colliders, and recent experimental and theoretical work on the quenching dynamics and PESs of NO­(A) + O 2 , N 2 , and CO. − …”

Reactive quenching of NO (A2Σ+) with H2O leads to HONO: a theoretical analysis of the reactive and nonreactive electronic quenching mechanisms

“…[18][19][20] Finally, Soulie ´and Paterson recently published a NO (A 2 S + ) + O 2 (X 3 S g À ) van der Waals PES, which contains a collision complex in an O-N-O-O linear geometry with an intermolecular distance of 4.3 Å and a binding energy of 95 cm À1 . 21 Three recent studies on NO (A 2 S + ) + O 2 are among the few that directly probe the mechanism of nonreactive electronic quenching of NO (A 2 S + ) with a molecular partner. In the first, Few and co-workers used time-resolved Fourier-transform infrared emission spectroscopy to measure vibrationally excited NO (X 2 P, n 00 = 2-22) produced through nonreactive electronic quenching.…”

“…18–20 Finally, Soulié and Paterson recently published a NO (A 2 Σ + ) + O 2 (X 3 Σ g − ) van der Waals PES, which contains a collision complex in an O–N–O–O linear geometry with an intermolecular distance of 4.3 Å and a binding energy of 95 cm −1 . 21…”