A theoretical study of the NH+NO reaction

Kimberly S. Bradley, Patrick McCabe, George C Schatz, Stephen P. Walch

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

We present a quasiclassical trajectory study of the NH+NO reaction using a global potential energy surface that is capable of describing branching to the H+N2O and OH+N2 products after initial formation of a HNNO intermediate complex. The surface is based on a many-body expansion wherein fragment potentials for the species N2H, HNO, and N2O are incorporated, using either previously developed potentials, or in the case of N2O, a newly developed potential. The three-body parts of these fragment potentials are damped in the four-body region to provide a zeroth order four-body surface, and then additional four-body terms and mapping transformations are applied to make the final four-body potential match the results of ab initio calculations for eight important HNNO stationary points (minima and saddle points) and for several reaction paths. In addition to this "best fit" surface (surface I), a second surface (surface II) is developed in which the ordering of the saddle points leading to formation of H+N2O and OH+N2 is reversed, and the energy release during 1,3 hydrogen migration is modified so that the N-N stretch experiences smaller distortions from N2 equilibrium during the reaction leading to OH+N2. Quasiclassical trajectory results on surface I show generally good correspondence with experiment, with a branching fraction of 13±3% for the formation of OH+N2 at 300 K, and relatively low OH and N 2 vibration/rotation excitation. The results on surface II are similar with respect to both branching and energy partitioning, indicating relatively weak sensitivity of the results of key features of the surface.

Original languageEnglish
Pages (from-to)6696-6705
Number of pages10
JournalJournal of Chemical Physics
Volume102
Issue number17
Publication statusPublished - 1995

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saddle points
Trajectories
fragments
trajectories
Potential energy surfaces
Hydrogen
potential energy
vibration
expansion
energy
sensitivity
hydrogen
products
excitation
Experiments

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Bradley, K. S., McCabe, P., Schatz, G. C., & Walch, S. P. (1995). A theoretical study of the NH+NO reaction. Journal of Chemical Physics, 102(17), 6696-6705.

A theoretical study of the NH+NO reaction. / Bradley, Kimberly S.; McCabe, Patrick; Schatz, George C; Walch, Stephen P.

In: Journal of Chemical Physics, Vol. 102, No. 17, 1995, p. 6696-6705.

Research output: Contribution to journalArticle

Bradley, KS, McCabe, P, Schatz, GC & Walch, SP 1995, 'A theoretical study of the NH+NO reaction', Journal of Chemical Physics, vol. 102, no. 17, pp. 6696-6705.
Bradley KS, McCabe P, Schatz GC, Walch SP. A theoretical study of the NH+NO reaction. Journal of Chemical Physics. 1995;102(17):6696-6705.
Bradley, Kimberly S. ; McCabe, Patrick ; Schatz, George C ; Walch, Stephen P. / A theoretical study of the NH+NO reaction. In: Journal of Chemical Physics. 1995 ; Vol. 102, No. 17. pp. 6696-6705.
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