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Computational investigation on the reaction of dimethyl ether with nitric dioxide. II. Detailed chemical kinetic modeling

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Abstract

Hydrogen abstraction from dimethyl ether (DME) by nitric dioxide (NO2) has been considered to be very sensitive to the DME ignition behavior. Thermal rate coefficients for the reaction of DME with NO2 are computed by employing the multi-structural canonical variational transition-state theory with multidimensional tunneling (MS-CVT/MT) at temperatures from 200 to 3000 K. The B2PLYP/TZVP theoretical level has been verified in the first part of this study against experiment for geometries of stationary points and against accurate CCSD(T)/CBS and CCSD(T)/6-311+G(2df,2p) computations for the energetics related to the title reaction, and then the compound CCSD(T)/6-311+G(2df,2p)//B2PLYP/TZVP computations are performed here to obtain the properties of all stationary points and the geometries, energies, gradients, and Hessians of non-stationary points along each reaction minimum-energy pathway. It has been proposed that the internal rotations in the transition structures are anharmonic and strongly coupled to each other to produce multiple conformations whose contributions are included in their partition function approximations. The previous evaluations for these rate coefficients based on transition-state theory with one-dimensional tunneling corrections and one-dimensional hindered rotor treatments of torsions are essentially distinct from our MS-CVT/SCT results where the critical effects of corner cutting due to small reaction-path curvature are seriously treated via multidimensional small-curvature tunneling (SCT) treatment and torsions are explicitly considered by multistructural treatments, and thus the MS-CVT/SCT rate coefficients are proposed particularly to refine the current kinetic model for DME combustion.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 21606178).

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  1. School of Chemical Engineering, Northwest University, Xi’an, 710069, China

    Yulei Guan, Ru Liu, Junpeng Lou, Haixia Ma & Jirong Song

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  1. Yulei Guan
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  2. Ru Liu
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Correspondence to Yulei Guan.

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214_2019_2516_MOESM1_ESM.doc

Part I. Optimized geometries, rotational constants, and unscaled frequencies for all TSa, TSb, and TSc structures using B2PLYP/TZVP level. The τ-i, τ-ii, τ-iii, and τ-iv potentials along their torsion coordinates fitted to the Fourier series of all TSa, TSb, and TSc structures are also included. Part II. Thermal rate coefficients for the channels R(a), R(b), and R(c) of the reaction of dimethyl ether with nitric dioxide. (DOC 1507 kb)

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Guan, Y., Liu, R., Lou, J. et al. Computational investigation on the reaction of dimethyl ether with nitric dioxide. II. Detailed chemical kinetic modeling. Theor Chem Acc 139, 1 (2020). https://doi.org/10.1007/s00214-019-2516-0

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