Combustion chemistry of methoxymethanol. Part I : Chemical kinetics of hydrogen-abstraction reactions and the unimolecular reactions of the product [C2H5O2] radicals
(2021) In Combustion and Flame 229.- Abstract
The reaction kinetics of hydrogen-abstraction reactions from methoxymethanol (CH3OCH2OH) by hydrogen (Ḣ) atom, hydroxyl (ȮH), hydroperoxyl (HȮ2), methyl (ĊH3) and methoxyl (CH3Ȯ) radicals, and decomposition of the related hydroxyl-methoxyl-methyl (CH3OĊHOH), hydroxymethoxyl-methyl (ĊH2OCH2OH) and methoxyl-methoxy (CH3OCH2Ȯ) radicals, have been investigated in this study through high-level ab initio calculations. The stationary points of the potential energy surfaces have been determined at the CCSD(T)/aug-cc-pVTZ level of theory corrected by MP2/aug-cc-pVT,QZ methods, based on the optimized geometries obtained from... (More)
The reaction kinetics of hydrogen-abstraction reactions from methoxymethanol (CH3OCH2OH) by hydrogen (Ḣ) atom, hydroxyl (ȮH), hydroperoxyl (HȮ2), methyl (ĊH3) and methoxyl (CH3Ȯ) radicals, and decomposition of the related hydroxyl-methoxyl-methyl (CH3OĊHOH), hydroxymethoxyl-methyl (ĊH2OCH2OH) and methoxyl-methoxy (CH3OCH2Ȯ) radicals, have been investigated in this study through high-level ab initio calculations. The stationary points of the potential energy surfaces have been determined at the CCSD(T)/aug-cc-pVTZ level of theory corrected by MP2/aug-cc-pVT,QZ methods, based on the optimized geometries obtained from BHandHLYP/6–311++G(d,p) method. Rate constants at temperatures from 300 to 2000 K for H-abstraction reactions by Ḣ atom, HȮ2, ĊH3 and CH3Ȯ radicals have been obtained using conventional transition state theory (TST), while those for H-abstraction reactions by ȮH radical have been calculated employing variation transition state theory (VTST). It is found that the H-abstraction reactions from the secondary carbon atom of methoxymethanol are the most favored pathways. Total rate constants for H-abstraction reactions by ȮH radical are the fastest among the title H-abstraction reactions at temperatures below 1000 K, while H-abstraction reactions by Ḣ atom are more competitive at temperatures above 1200 K. Pressure-dependent rate constants at temperatures in the range of 300–2000 K and at pressures from 0.01 to 100 atm for the unimolecular reactions of CH3OĊHOH, ĊH2OCH2OH and CH3OCH2Ȯ radicals have been obtained from Rice-Ramsperger-Kassel-Marcus/Master Equation (RRKM/ME) calculations. Temperature-dependent thermochemical properties for methoxymethanol and related radicals have been computed using a combination of composite methods.
(Less)
- author
- Zhu, Yuxiang ; Zhou, Chong Wen and Konnov, Alexander A. LU
- organization
- publishing date
- 2021-07-01
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- Ab initio calculations, Hydrogen abstraction, Kinetics, Methoxymethanol
- in
- Combustion and Flame
- volume
- 229
- article number
- 111396
- publisher
- Elsevier
- external identifiers
-
- scopus:85102750079
- ISSN
- 0010-2180
- DOI
- 10.1016/j.combustflame.2021.111396
- language
- English
- LU publication?
- yes
- additional info
- .
- id
- 435c88c6-1726-4ce5-85ae-f139ed700dc6
- date added to LUP
- 2021-04-01 10:35:03
- date last changed
- 2022-04-27 01:14:56
@article{435c88c6-1726-4ce5-85ae-f139ed700dc6,
abstract = {{<p>The reaction kinetics of hydrogen-abstraction reactions from methoxymethanol (CH<sub>3</sub>OCH<sub>2</sub>OH) by hydrogen (Ḣ) atom, hydroxyl (ȮH), hydroperoxyl (HȮ<sub>2</sub>), methyl (ĊH<sub>3</sub>) and methoxyl (CH<sub>3</sub>Ȯ) radicals, and decomposition of the related hydroxyl-methoxyl-methyl (CH<sub>3</sub>OĊHOH), hydroxymethoxyl-methyl (ĊH<sub>2</sub>OCH<sub>2</sub>OH) and methoxyl-methoxy (CH<sub>3</sub>OCH<sub>2</sub>Ȯ) radicals, have been investigated in this study through high-level ab initio calculations. The stationary points of the potential energy surfaces have been determined at the CCSD(T)/aug-cc-pVTZ level of theory corrected by MP2/aug-cc-pVT,QZ methods, based on the optimized geometries obtained from BHandHLYP/6–311++G(d,p) method. Rate constants at temperatures from 300 to 2000 K for H-abstraction reactions by Ḣ atom, HȮ<sub>2</sub>, ĊH<sub>3</sub> and CH<sub>3</sub>Ȯ radicals have been obtained using conventional transition state theory (TST), while those for H-abstraction reactions by ȮH radical have been calculated employing variation transition state theory (VTST). It is found that the H-abstraction reactions from the secondary carbon atom of methoxymethanol are the most favored pathways. Total rate constants for H-abstraction reactions by ȮH radical are the fastest among the title H-abstraction reactions at temperatures below 1000 K, while H-abstraction reactions by Ḣ atom are more competitive at temperatures above 1200 K. Pressure-dependent rate constants at temperatures in the range of 300–2000 K and at pressures from 0.01 to 100 atm for the unimolecular reactions of CH<sub>3</sub>OĊHOH, ĊH<sub>2</sub>OCH<sub>2</sub>OH and CH<sub>3</sub>OCH<sub>2</sub>Ȯ radicals have been obtained from Rice-Ramsperger-Kassel-Marcus/Master Equation (RRKM/ME) calculations. Temperature-dependent thermochemical properties for methoxymethanol and related radicals have been computed using a combination of composite methods.</p>}},
author = {{Zhu, Yuxiang and Zhou, Chong Wen and Konnov, Alexander A.}},
issn = {{0010-2180}},
keywords = {{Ab initio calculations; Hydrogen abstraction; Kinetics; Methoxymethanol}},
language = {{eng}},
month = {{07}},
publisher = {{Elsevier}},
series = {{Combustion and Flame}},
title = {{Combustion chemistry of methoxymethanol. Part I : Chemical kinetics of hydrogen-abstraction reactions and the unimolecular reactions of the product [C<sub>2</sub>H<sub>5</sub>O<sub>2</sub>] radicals}},
url = {{http://dx.doi.org/10.1016/j.combustflame.2021.111396}},
doi = {{10.1016/j.combustflame.2021.111396}},
volume = {{229}},
year = {{2021}},
}