Ab initio kinetics studies of hydrogen atom abstraction from methyl propanoate

Physical Chemistry Chemical Physics : PCCP
Ting TanEmily A Carter

Abstract

The kinetics of hydrogen abstraction by five radicals (H, CH3, O((3)P), OH, and HO2) from a biodiesel surrogate, methyl propanoate (MP), is theoretically investigated. We employ high-level ab initio quantum chemistry methods, coupled-cluster singles and doubles with perturbative triples correction (CCSD(T)) and multi-reference singles and doubles configuration interaction (MRSDCI) with the Davidson-Silver (DS) correction, and obtain chemically accurate reaction energetics. Overall, MRSDCI + DS predicts comparable energetics to CCSD(T) for MP + H/CH3/O/OH. The rate constants are computed using transition state theory (TST-Rice-Ramsperger-Kassel-Marcus theory) in conjunction with the separable-hindered-rotor approximation, variable reaction coordinate TST, and the multi-structure all-structure (MS-AS) approach. A simplified method, semi-multi-structure, is also employed for MP + OH/HO2, and the rate coefficients with this less expensive method are in good agreement with the results obtained with the MS-AS method. The fitted modified Arrhenius expressions are provided over a temperature range of 250 to 2000 K. The predicted rate coefficients for MP + OH agree remarkably well with experimental data over a wide temperature range. Br...Continue Reading

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Citations

Jun 13, 2018·Physical Chemistry Chemical Physics : PCCP·Hongbo NingAamir Farooq
Feb 15, 2020·Physical Chemistry Chemical Physics : PCCP·Martina BaroncelliHeinz Pitsch
Sep 14, 2019·Physical Chemistry Chemical Physics : PCCP·Yanlei ShangSheng-Nian Luo
Nov 12, 2020·The Journal of Physical Chemistry. a·Aric C RoussoNils Hansen
Mar 22, 2019·The Journal of Physical Chemistry. a·Yawei Chi, Xiaoqing You

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