A quantum chemical investigation of possible intermediates in the reaction of the amidogen and hydroperoxyl radicals

Sumathi, R.; Engels, Bernd; Peyerimhoff, S. D.
November 1996
Journal of Chemical Physics;11/8/1996, Vol. 105 Issue 18, p8117
Academic Journal
The reaction NH2+HO2→products, a reaction of atmospheric interest, has been studied using ab initio molecular orbital calculations with extended basis sets [6-311++G** and 6-311++G(2df,2pd)], and a variety of methods accounting for electron correlation such as second order Mo\ller–Plesset perturbation theory (MP2) with all electrons, quadratic configuration interaction singles and doubles with triples correction [QCISD(T)], complete active space [CAS(8,8)], and multireference double excitation configuration interaction (MRDCI). Also, the performance of density functional (DFT) calculations has been investigated. In the present study, all stationary points on various potential energy surfaces giving rise to different products, HNO+H2O, NH2O+OH, NH3+O2, H2O2+NH, and HNOO+H2, have been optimized and characterized by their Hessian matrix. Amine oxide and dihydroxyamine have been found to be the precursors for HNO formation. In addition, the paper attempts to explain the experimental finding, nonobservation of OH· during photolysis of ammonia, and it demands new experiments with spectroscopic identification of OH radicals. © 1996 American Institute of Physics.


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