title: Dynamics study of the OH + NH3 hydrogen abstraction reaction using QCT calculations based on an analytical potential energy surface.
abstract: To understand the reactivity and mechanism of the OH + NH3 → H2O + NH2 gas-phase reaction, which evolves through wells in the entrance and exit channels, a detailed dynamics study was carried out using quasi-classical trajectory calculations. The calculations were performed on an analytical potential energy surface (PES) recently developed by our group, PES-2012 [Monge-Palacios et al. J. Chem. Phys. 138, 084305 (2013)]. Most of the available energy appeared as H2O product vibrational energy (54%), reproducing the only experimental evidence, while only the 21% of this energy appeared as NH2 co-product vibrational energy. Both products appeared with cold and broad rotational distributions. The excitation function (constant collision energy in the range 1.0-14.0 kcal mol(-1)) increases smoothly with energy, contrasting with the only theoretical information (reduced-dimensional quantum scattering calculations based on a simplified PES), which presented a peak at low collision energies, related to quantized states. Analysis of the individual reactive trajectories showed that different mechanisms operate depending on the collision energy. Thus, while at high energies (E(coll) ≥ 6 kcal mol(-1)) all trajectories are direct, at low energies about 20%-30% of trajectories are indirect, i.e., with the mediation of a trapping complex, mainly in the product well. Finally, the effect of the zero-point energy constraint on the dynamics properties was analyzed.
authors.affiliation: Departamento de Química Física, Universidad de Extremadura, 06071 Badajoz, Spain.
authors.forename: M
authors.initials: M
authors.lastname: Monge-Palacios
authors.forename: J C
authors.initials: JC
authors.lastname: Corchado
authors.forename: J
authors.initials: J
authors.lastname: Espinosa-Garcia
mesh_terms: D000641:Ammonia / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D006878:Hydroxides / Q000737:chemistry*; D011789:Quantum Theory; D013499:Surface Properties; D013816:Thermodynamics
chemical_list: D006878:Hydroxides; D000641:Ammonia; D006859:Hydrogen; C031356:hydroxide ion