Authors: Adriana Caracciolo | Juan Carlos San Vincente Veliz | Dandan Lü | Hua Guo | Markus Meuwly | Timothy K. Minton
Source: ChemRxiv (preprint, 2023-07-05)
Field: Chemistry — Spectroscopy

Experimental and Theoretical Studies of Hyperthermal N + O2 Collisions 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 Ecoll = 77.5 kcal mol-1, with velocity- and angle-resolved product detection by a rotatable mass spectrometer detector. Non-reactive (N + O2) and reactive (NO + O) product channels were identified. In the c.m. reference frame, the non-reactively 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 (Eavl = 77.5 kcal mol-1) was retained in translation of the non-reactive products (N + O2), whereas a much smaller fraction of the available energy for the reactive pathway (Eavl = 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 Ecoll = 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 multi-reference 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 non-reactive N + O2 products matched the experimental translational energy and angular distributions almost quantitatively. Finally, relative yields for the non-reactive and reactive scattering channels were determined from the experiment and from both theoretical methods, and all results are in reasonable agreement. Chemistry ; Atomic physics ; Excitation ; Molecule ; Product (mathematics) ; Reproducing kernel Hilbert space ; Translational energy ; Energy (signal processing) ; Analytical Chemistry (journal) ; Molecular physics ; Hilbert space ; Physics ; Computational chemistry ; Geometry ; Quantum mechanics Spectroscopy and Laser Applications ; Advanced Chemical Physics Studies ; Atmospheric chemistry and aerosols