Experimental and Theoretical Studies of Hyperthermal N + O₂ Collisions

Abstract

The dynamics of hyperthermal N­(4S) + O2 collisions were investigated both experimentally and theoretically. Crossed molecular beams experiments were performed at an average center-of-mass (c.m.) collision energy of ⟨E coll⟩ = 77.5 kcal mol–1, with velocity- and angle-resolved product detection by a rotatable mass spectrometer detector. Nonreactive (N + O2) and reactive (NO + O) product channels were identified. In the c.m. reference frame, the nonreactively scattered N atoms and reactively scattered NO molecules were both directed into the forward direction with respect to the initial direction of the reagent N atoms. On average, more than 90% of the available energy (⟨E avl⟩ = 77.5 kcal mol–1) was retained in translation of the nonreactive products (N + O2), whereas a much smaller fraction of the available energy for the reactive pathway (⟨E avl⟩ = 109.5 kcal mol–1) went into translation of the NO + O products, and the distribution of translational energies for this channel was broad, indicating extensive internal excitation in the nascent NO molecules. The experimentally derived c.m. translational energy and angular distributions of the reactive products suggested at least two dynamical pathways to the formation of NO + O. Quasiclassical trajectory (QCT) calculations were performed with a collision energy of E coll = 77 kcal mol–1 using two sets of potential energy surfaces, denoted as PES-I and PES-II, and these theoretical results were compared to each other and to the experimental results. PES-I is a reproducing kernel Hilbert space (RKHS) representation of multireference configurational interaction (MRCI) energies, while PES-II is a many-body permutation invariant polynomial (MB-PIP) fit of complete active space second order perturbation (CASPT2) points. The theoretical investigations were both consistent with the experimental suggestion of two dynamical pathways to produce NO + O, where reactive collisions may proceed on the doublet (12A′) and quartet (14A′) surfaces. When analyzed with this theoretical insight, the experimental c.m. translational energy and angular distributions were in reasonably good agreement with those predicted by the QCT calculations, although minor differences were observed which are discussed. Theoretical translational energy and angular distributions for the nonreactive N + O2 products matched the experimental translational energy and angular distributions almost quantitatively. Finally, relative yields for the nonreactive and reactive scattering channels were determined from the experiment and from both theoretical methods, and all results are in reasonable agreement.

Spiers Memorial Lecture: New directions in molecular scattering

“…405 Recent gas-phase reactions have focused on reactions that are important in hypersonics, including N + O 2 (ref. 406) and O + NO, 407 where it is possible to use the results to validate reaction dynamics calculations with high-quality PESs, and then the calculations can be used to generate rate coefficients that are crucial for atmospheric modelers. The gassurface hyperthermal beam studies have also been used to provide insights about the structure of ionic-liquid interfaces, 408,409 and about processes that are important for degradation of hypersonic and space vehicle components.…”

“…This regime can be effectively studied using quasi-classical trajectory methods, but with signicant challenges in the treatment of multiple electronic states and their couplings. 406 The future of surface chemistry involves understanding reaction mechanisms under the high temperature and pressure conditions where real catalysis takes place; both theoretical and experimental reaction kinetics will be essential (https://doi.org/10.1039/D3FD00174A). Micro-kinetic modeling forms the underlying mathematical framework of catalysis, and to establish a fundamental foundation, existing rate theories must be improved 395 and new ones must be developed.…”