Potential energy surface of the à state of NH2 and the role of excited states in the N(2D) + H2 reaction

Lisa A. Pederson, George C Schatz, Timothy Hollebeek, Tak San Ho, Herschel Rabitz, Lawrence B. Harding

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Abstract

We present a global potential energy surface for the à state of NH2 (12A') based on application of the reproducing kernel Hilbert space (RKHS) interpolation method to high-quality ab initio (multireference configuration-interaction) results. This surface correlates adiabatically to the a1 Δ state of NH, with a reaction endoergicity of about 8 kcal/mol, but it can also lead to formation of ground-state NH (exoergic by 29 kcal/ mol) via nonadiabatic (Renner-Teller) interactions for linear HNH geometries that lie near the bottom of a 94 kcal/mol deep well that is accessible from N(2D) + H2 by insertion over a 3.4 kcal/mol barrier. This insertion barrier is about 1 kcal/mol higher in energy than the corresponding insertion barrier associated with the ground state of NH2(12A"). As a result, the à state contributes measurably to both the thermal rate constant for N(2D) + H2 and the rate for NH(a1Δ) production. Extensive quasiclassical trajectory calculations are performed on the RKHS surface to study the N(2D) + H2 reaction dynamics, with the nonadiabatic rate constant estimated using a capture model. We find that the cross section for ground-state NH production is comparable to that obtained on the ground-state 1A" surface, except for a 1 kcal/mol shift upward in the effective threshold due to the different barrier height. The cross section for NH(a1Δ) production has a higher threshold energy and is about 15% of the ground-state cross section at energies well above threshold.

Original languageEnglish
Pages (from-to)2301-2307
Number of pages7
JournalJournal of Physical Chemistry A
Volume104
Issue number11
Publication statusPublished - Mar 23 2000

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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    Pederson, L. A., Schatz, G. C., Hollebeek, T., Ho, T. S., Rabitz, H., & Harding, L. B. (2000). Potential energy surface of the à state of NH2 and the role of excited states in the N(2D) + H2 reaction. Journal of Physical Chemistry A, 104(11), 2301-2307.