A master equation simulation for the • OH + CH 3 OH reaction

Nguyen, Thanh Lam; Ruscic, Branko; Stanton, John F.

doi:10.1063/1.5081827

Title: A master equation simulation for the ^• OH + CH ₃ OH reaction

Journal Article · Mon Feb 25 00:00:00 EST 2019 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5081827· OSTI ID:1503282

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Univ. of Florida, Gainesville, FL (United States)
Argonne National Laboratory (ANL),Lemont, IL (United States)

A combined (fixed-J) two-dimensional master-equation / semi-classical transition state theory / variational Rice-Ramsperger-Kassel-Marcus (2DME/SCTST/vRRKM) approach has been used to compute reaction rate coefficients of •OH with CH₃OH over a wide range of temperatures (10 - 2500 K) and pressures (10^-1-10⁴ Torr) based on a potential energy surface that has been constructed using a modification of the HEAT thermochemical protocol. The calculated results show that the title reaction is nearly pressure-independent when T > 250 K, but depends strongly on pressure at lower temperatures. Also, the preferred mechanism and rate constants are found to be very sensitive to temperature. The reaction pathway CH₃OH + ^•OH → CH₃O^• + H₂O proceeds exclusively through tunneling at exceedingly low temperatures (T ≤50 K) typical of those established in interstellar environments. In this regime, the rate constant is found to increase with decreasing temperature, which agrees with low-temperature experimental results. The thermodynamically favored reaction pathway CH₃OH + ^•OH → ^•CH₂OH + H₂O becomes dominant at higher temperatures (T ≥ 200 K), such as those found in Earth’s atmosphere as well as combustion environments. By modifying the ab initio barrier heights slightly, experimental rate constants from 200 to 1250 K can be satisfactorily reproduced.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: AC02-06CH11357; FG02-07ER15884

OSTI ID:: 1503282

Journal Information:: Journal of Chemical Physics, Vol. 150, Issue 8; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 28 works

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Title: A master equation simulation for the • OH + CH 3 OH reaction

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Title: A master equation simulation for the ^• OH + CH ₃ OH reaction