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Title: Adventures on the C 3H 5O potential energy surface: OH+propyne, OH+allene and related reactions

We mapped out the stationary points and the corresponding conformational space on the C 3H 5O potential energy surface relevant for the OH + allene and OH + propyne reactions systematically and automatically using the KinBot software at the UCCSD(T)-F12b/cc-pVQZ-F12//M06-2X/6-311++G(d,p) level of theory. We used RRKM-based 1-D master equations to calculate pressure- and temperature-dependent, channel-specific phenomenological rate coefficients for the bimolecular reactions propyne + OH and allene + OH, and for the unimolecular decomposition of the CH 3CCHOH, CH 3C(OH)CH, CH 2CCH 2OH, CH 2C(OH)CH 2 primary adducts, and also for the related acetonyl, propionyl, 2-methylvinoxy, and 3-oxo-1-propyl radicals. The major channel of the bimolecular reactions at high temperatures is the formation propargyl + H 2O, which makes the title reactions important players in soot formation at high temperatures. However, below ~1000 K the chemistry is more complex, involving the competition of stabilization, isomerization and dissociation processes. We found that the OH addition to the central carbon of allene has a particularly interesting and complex pressure dependence, caused by the low-lying exit channel to form ketene + CH 3 bimolecular products. In this study, we compared our results to a wide range of experimental data and assessed possible uncertainties arisingmore » from certain aspects of the theoretical framework.« less
Authors:
ORCiD logo [1] ;  [2]
  1. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Report Number(s):
SAND-2013-10363J
Journal ID: ISSN 1540-7489; PII: S1540748914001060
Grant/Contract Number:
AC04-94AL85000
Type:
Accepted Manuscript
Journal Name:
Proceedings of the Combustion Institute
Additional Journal Information:
Journal Volume: 35; Journal Issue: 1; Journal ID: ISSN 1540-7489
Publisher:
Elsevier
Research Org:
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Sponsoring Org:
USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; pressure dependence; propargyl; master equation
OSTI Identifier:
1122136
Alternate Identifier(s):
OSTI ID: 1251901

Zádor, Judit, and Miller, James A. Adventures on the C3H5O potential energy surface: OH+propyne, OH+allene and related reactions. United States: N. p., Web. doi:10.1016/j.proci.2014.05.103.
Zádor, Judit, & Miller, James A. Adventures on the C3H5O potential energy surface: OH+propyne, OH+allene and related reactions. United States. doi:10.1016/j.proci.2014.05.103.
Zádor, Judit, and Miller, James A. 2014. "Adventures on the C3H5O potential energy surface: OH+propyne, OH+allene and related reactions". United States. doi:10.1016/j.proci.2014.05.103. https://www.osti.gov/servlets/purl/1122136.
@article{osti_1122136,
title = {Adventures on the C3H5O potential energy surface: OH+propyne, OH+allene and related reactions},
author = {Zádor, Judit and Miller, James A.},
abstractNote = {We mapped out the stationary points and the corresponding conformational space on the C3H5O potential energy surface relevant for the OH + allene and OH + propyne reactions systematically and automatically using the KinBot software at the UCCSD(T)-F12b/cc-pVQZ-F12//M06-2X/6-311++G(d,p) level of theory. We used RRKM-based 1-D master equations to calculate pressure- and temperature-dependent, channel-specific phenomenological rate coefficients for the bimolecular reactions propyne + OH and allene + OH, and for the unimolecular decomposition of the CH3CCHOH, CH3C(OH)CH, CH2CCH2OH, CH2C(OH)CH2 primary adducts, and also for the related acetonyl, propionyl, 2-methylvinoxy, and 3-oxo-1-propyl radicals. The major channel of the bimolecular reactions at high temperatures is the formation propargyl + H2O, which makes the title reactions important players in soot formation at high temperatures. However, below ~1000 K the chemistry is more complex, involving the competition of stabilization, isomerization and dissociation processes. We found that the OH addition to the central carbon of allene has a particularly interesting and complex pressure dependence, caused by the low-lying exit channel to form ketene + CH3 bimolecular products. In this study, we compared our results to a wide range of experimental data and assessed possible uncertainties arising from certain aspects of the theoretical framework.},
doi = {10.1016/j.proci.2014.05.103},
journal = {Proceedings of the Combustion Institute},
number = 1,
volume = 35,
place = {United States},
year = {2014},
month = {6}
}