Product branching fractions in the reaction of NH (ND) ([sup 3][Sigma][sup [minus]]) with NO

Journal Article · Thu Jan 13 04:00:00 EST 1994 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100053a028· OSTI ID:5153714

Durant, Jr, J L ^[1]

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1. Sandia National Lab., Livermore, CA (United States)

We have carried out a combined experimental and theoretical study of the reaction of NH (ND) ([sup 3][Sigma][sup [minus]]) with NO aimed at understanding the product distribution from that reaction. The reaction was studied at room temperature using the discharge flow technique with mass spectrometric detection of the reaction products. Measured product branching fractions at room temperature for production of N[sub 2]O + H (D) were 0.8 [+-] 0.4 for NH ([sup 3][Sigma][sup [minus]]) + NO and 0.87 [+-] 0.17 for ND ([sup 3][Sigma][sup [minus]]) + NO (1 [sigma] statistical errors). Stationary points on the HNNO [sup 2]A[prime] potential energy surface were characterized using the Gaussian 2 ab initio method. The initial addition of NH([sup 3][Sigma][sup [minus]]) to NO on the [sup 2]A[prime] surface is predicted to proceed without a barrier to form trans-HNNO; reaction to produce the cis isomer is predicted to have a barrier of 2.9 kcal/mol. The cis- and trans-HNNO are predicted to be at -48.9 and -56.0 kcal/mol relative to the separated reactants. Transition states with energies of -25.3 and -17.9 kcal/mol were located for dissociation of the cis isomer into H + N[sub 2]O and OH + N[sub 2], respectively. The transition state for interconversion of the isomers was calculated to be at approximately -30.8 kcal/mol. The trans-HNNO was found to isomerize to the cis form before decomposing. The potential energy surface calculated explains the major features of the reaction. 31 refs., 1 fig., 4 tabs.

• OSTI ID: 5153714
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 98:2; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
ADDUCTS
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMBUSTION
DATA
DEUTERIDES
DEUTERIUM COMPOUNDS
DISSOCIATION
ENERGY
FLAMES
FORECASTING
FUNCTIONS
GAUSS FUNCTION
HYDRIDES
HYDROGEN COMPOUNDS
INFORMATION
KINETICS
MASS SPECTROSCOPY
MATHEMATICAL MODELS
NITRIC OXIDE
NITROGEN COMPOUNDS
NITROGEN HYDRIDES
NITROGEN OXIDES
NITROUS OXIDE
NUMERICAL DATA
OXIDATION
OXIDES
OXYGEN COMPOUNDS
POTENTIAL ENERGY
RADICALS
REACTION KINETICS
SPECTROSCOPY
THEORETICAL DATA
THERMOCHEMICAL PROCESSES
THERMODYNAMICS