A master equation simulation for the • OH + CH 3 OH reaction
Abstract
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.
- Authors:
-
- Univ. of Florida, Gainesville, FL (United States)
- Argonne National Laboratory (ANL),Lemont, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1503282
- Grant/Contract Number:
- AC02-06CH11357; FG02-07ER15884
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 150; Journal Issue: 8; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; astrochemistry; combustion; electronic structure methods; elementary reactions; kinetics; master equation; partition function; thermochemistry
Citation Formats
Nguyen, Thanh Lam, Ruscic, Branko, and Stanton, John F. A master equation simulation for the • OH + CH 3 OH reaction. United States: N. p., 2019.
Web. doi:10.1063/1.5081827.
Nguyen, Thanh Lam, Ruscic, Branko, & Stanton, John F. A master equation simulation for the • OH + CH 3 OH reaction. United States. https://doi.org/10.1063/1.5081827
Nguyen, Thanh Lam, Ruscic, Branko, and Stanton, John F. Mon .
"A master equation simulation for the • OH + CH 3 OH reaction". United States. https://doi.org/10.1063/1.5081827. https://www.osti.gov/servlets/purl/1503282.
@article{osti_1503282,
title = {A master equation simulation for the • OH + CH 3 OH reaction},
author = {Nguyen, Thanh Lam and Ruscic, Branko and Stanton, John F.},
abstractNote = {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.},
doi = {10.1063/1.5081827},
journal = {Journal of Chemical Physics},
number = 8,
volume = 150,
place = {United States},
year = {Mon Feb 25 00:00:00 EST 2019},
month = {Mon Feb 25 00:00:00 EST 2019}
}
Web of Science
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