Quasiclassical Trajectory Calculations of the N((2)D) + H2O Reaction Elucidating the Formation Mechanism of HNO and HON Seen in Molecular Beam Experiments.
The N((2)D) + H2O is a reaction with competitive product channels, passing through several intermediates. Dynamics of this reaction had been investigated by two of the present authors at two collision energies, Ec, using the crossed molecular beams mass spectrometric method ( Faraday Discuss. 2001 , 119 , 27 - 49 ). The complicated mechanism of this reaction and puzzling results encouraged us to investigate the reaction in a joint experimental/theoretical study. Quasiclassical trajectory (QCT) calculations on an ab initio potential energy surface describing all channels of the title reaction are done with a focus on the N/H exchange channels. Interesting results of QCT calculations, in very good agreement with experimental data, reveal subtle details of the reaction dynamics of the title reaction to HNO/HON + H exit channels by disentangling the different routes to formation of the two possible HNO/HON isomers and therefore assisting in a critical manner the derivation of the reaction mechanism. Results of the present study show that the nonstatistical HNOH intermediate governs exit channels; therefore, the HON channel is as important as that of HNO. The study also confirms that the H2 + NO molecular channel is negligible even though the barrier to its formation is calculated to be well below the reactant asymptote.
†Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, Georgia 30322, United States.
Zahra
Z
Homayoon
†Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, Georgia 30322, United States.
Joel M
JM
Bowman
‡Dipartimento di Chimica, Biologia e Biotecnologie, Università degli Studi di Perugia, 06123 Perugia, Italy.
Nadia
N
Balucani
‡Dipartimento di Chimica, Biologia e Biotecnologie, Università degli Studi di Perugia, 06123 Perugia, Italy.
Piergiorgio
P
Casavecchia
N(2D) reactions; crossed molecular beams; isomers; nonstatistical dynamics; quasiclassical trajectories; reaction dynamics