Imaging the nonreactive collisional quenching dynamics of NO (A2Σ+) radicals with O2 (X3Σg -).

Abstract

Nitric oxide (NO) radicals are ubiquitous chemical intermediates present in the atmosphere and in combustion processes, where laser-induced fluorescence is extensively used on the NO (A2Σ+ ← X2Π) band to report on fuel-burning properties. However, accurate fluorescence quantum yields and NO concentration measurements are impeded by electronic quenching of NO (A2Σ+) to NO (X2Π) with colliding atomic and molecular species. To improve predictive combustion models and develop a molecular-level understanding of NO (A2Σ+) quenching, we report the velocity map ion images and product state distributions of NO (X2Π, v″ = 0, J″, Fn, Λ) following nonreactive collisional quenching of NO (A2Σ+) with molecular oxygen, O2 (X3Σg -). A novel dual-flow pulse valve nozzle is constructed and implemented to carry out the NO (A2Σ+) electronic quenching studies and to limit NO2 formation. The isotropic ion images reveal that the NO-O2 system evolves through a long-lived NO3 collision complex prior to formation of products. Furthermore, the corresponding total kinetic energy release distributions support that O2 collision coproducts are formed primarily in the c1Σu - electronic state with NO (X2Π, v″ = 0, J″, Fn, Λ). The product state distributions also indicate that NO (X2Π) is generated with a propensity to occupy the Π(A″) Λ-doublet state, which is consistent with the NO π* orbital aligned perpendicular to nuclear rotation. The deviations between experimental results and statistical phase space theory simulations illustrate the key role that the conical intersection plays in the quenching dynamics to funnel population to product rovibronic levels.