Abstract
Quasi-classical trajectory calculations and stochastic one-dimensional chemical master equation simulation methods are used to study the dynamics of the reaction of amidogen radical [NH2(2B1)] with hydroperoxyl radical [HO2(2A″)] on the lowest singlet electronic state. The title complex reaction takes place on a multi-well multichannel potential energy surface consisting of three deep potential wells and one van der Waals complex. In quasi-classical trajectory calculations a new analytical potential energy surface based on CCSD(T)/aug-cc-pVTZ//MPW1K/6-31+G(d,p) ab initio method was driven and used to study the dynamics of the title reaction. In quasi-classical trajectory calculations, the reactive cross sections and reaction probabilities are determined for 200–2000 K relative translational energies to calculate the rate constants. The same ab initio method was used to have the necessary data for solving the one-dimensional chemical master equation to calculate the rate constants of different channels. In solving the master equation, the Lennard-Jones potential model was used to form the collision between the collider gases. The fractional populations of different intermediates and products in the early stages of the reaction were examined to determine the role of the energized intermediates and the van der Waals complex on the dynamics of the title reaction. Although the calculated total rate constants from both methods are in good agreement with the reported experimental values in the literature, the quasi-classical trajectory simulation predicts the formation of NH2O + OH as the major channel in the title reaction in accordance with the previous studies (Sumathi and Peyerimhoff, Chem. Phys. Lett., 263:742–748, 1996), while the stochastic master equation simulation predicts the formation of HNO + H2O as the major products.
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This work was supported by the Research Council of Shiraz University.
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Vibrational term values and moments of inertia of the stationary points calculated at the MPW1K/6-31+G(d,p) level of theory are listed in Table S1. Parameters for the analytical potential energy surface in equation (5) are shown in Tables S2 to S4. Numbering of the atoms related to the analytical potential energy surface is shown in Figure S1. The Supporting Information is available free of charge on the JICS Publications website. (DOCX 117 kb)
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Mousavipour, S.H., Keshavarz, F. & Soleimanzadegan, S. A theoretical study on the dynamics of the gas phase reaction of NH2(2B1) with HO2(2A″). J IRAN CHEM SOC 13, 1115–1124 (2016). https://doi.org/10.1007/s13738-016-0825-y
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DOI: https://doi.org/10.1007/s13738-016-0825-y