Theoretical characterization of the reaction NH2+NO→products

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Abstract
The potential energy surface for NH2+NO has been characterized using complete active space self‐consistent‐field (CASSCF)/derivative calculations to determine the stationary point geometries and frequencies followed by internally contracted configuration interaction (ICCI) calculations to determine the energetics. Production of N2+H2O is found to involve a complex mechanism. The initially formed NH2NO undergoes a 1,3‐hydrogen shift to give an HNNOH isomer (with the substituents trans about the NN bond and cis about the NO bond) which undergoes subsequent cis–trans isomerizations about the NN and NO bonds before decomposing to N2+H2O. The saddle point for production of N2+H2O has an approximately rectangular arrangement of one H atom, the two N atoms, and the O atom. This process does not involve a barrier with respect to NH2+NO. Formation of HN2+OH can occur from any of the isomers of HNNOH with no barrier, but the overall process is endothermic by 0.7 kcal/mol [based on the computed Δ Hf0 (0 K) of HN2]. The results obtained in this work are qualitatively the same as previous work, but both the stationary point geometries and energies should be more reliable due to the use of larger basis sets and more extensive inclusion of electron correlation effects.

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