title: Theoretical kinetics study of the F((2)P) + NH3 hydrogen abstraction reaction.
abstract: The hydrogen abstraction reaction of fluorine with ammonia represents a true chemical challenge because it is very fast, is followed by secondary abstraction reactions, which are also extremely fast, and presents an experimental/theoretical controversy about rate coefficients. Using a previously developed full-dimensional analytical potential energy surface, we found that the F + NH3 → HF + NH2 system is a barrierless reaction with intermediate complexes in the entry and exit channels. In order to understand the reactivity of the title reaction, thermal rate coefficidents were calculated using two approaches: ring polymer molecular dynamics and quasi-classical trajectory calculations, and these were compared with available experimental data for the common temperature range 276-327 K. The theoretical results obtained show behavior practically independent of temperature, reproducing Walther-Wagner's experiment, but in contrast with Persky's more recent experiment. However, quantitatively, our results are 1 order of magnitude larger than those of Walther-Wagner and reasonably agree with the Persky at the lowest temperature, questioning so Walther-Wagner's older data. At present, the reason for this discrepancy is not clear, although we point out some possible reasons in the light of current theoretical calculations.
authors.affiliation: Departamento de Química Física, Universidad de Extremadura , 06071 Badajoz, Spain.
authors.forename: J
authors.initials: J
authors.lastname: Espinosa-Garcia
authors.forename: A
authors.initials: A
authors.lastname: Fernandez-Ramos
authors.forename: Y V
authors.initials: YV
authors.lastname: Suleimanov
authors.forename: J C
authors.initials: JC
authors.lastname: Corchado
mesh_terms: D000641:Ammonia / Q000737:chemistry*; D005461:Fluorine / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D007700:Kinetics; D056004:Molecular Dynamics Simulation; D013696:Temperature
chemical_list: D005461:Fluorine; D000641:Ammonia; D006859:Hydrogen