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Effects of Anharmonicity, Recrossing, Tunneling, and Pressure on the H‑Abstractions from Dimethylamine by Triplets O and O2
datasetposted on 2022-02-08, 22:14 authored by Yanlei Shang, Hongbo Ning, Jinchun Shi, Yi Wu, Sheng-Nian Luo
Rate constants of the H-abstraction reactions from dimethylamine (DMA) by triplets O and O2 are theoretically determined with the canonical variational transition-state theory (CVT). By comparing the barrier heights and reaction energies obtained from different density-functional theory methods to those computed from the gold-standard method CCSD(T)/CBS(T-Q), we identify the M08-HX/ma-TZVP method as the best with a mean unsigned deviation of 1.0 kcal mol–1. On the basis of the optimized geometries and frequencies with the selected method, the rate constants are calculated using the CVT method combined with the multistructural torsional anharmonicity and small-curvature tunnelling (MS-CVT/SCT) options in the temperature range 200–2000 K. The calculations show that OH and HO2 are mainly produced from the direct abstraction from the C–H bond. The multistructural torsional anharmonicity has a large contribution to the rate constants, and the effects of recrossing and tunneling at the N-site are more important than those at C-site. Additionally, given the formation of reactant complex between DMA and triplet O, the H-abstraction channel is not favored at high pressure. Our calculations with both the Polyrate and MESS codes agree with the reported data within the uncertainty.
reported data withinreaction energies obtainedmess codes agreemean unsigned deviationcanonical variational transition0 kcal mol)/ cbs (functional theory methodsmultistructural torsional anharmonicityh ‑ abstractions2 subcvt method combinedstate theorytzvp methodselected methodtheoretically determinedreactant complexrate constantsq ),optimized geometriesmainly producedlarge contributiondirect abstractiondifferent densitycvt ).curvature tunnellingcalculated usingbarrier heightsabstraction reactionsabstraction channel