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Adventures on the C3H5O potential energy surface: OH+propyne, OH+allene and related reactions

Journal Article · · Proceedings of the Combustion Institute
 [1];  [2]
  1. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
+ Show Author Affiliations
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.
Research Organization:
Sandia National Laboratories (SNL-CA), Livermore, CA (United States)
Sponsoring Organization:
USDOE; USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC02-06CH11357; AC04-94AL85000
OSTI ID:
1122136
Alternate ID(s):
OSTI ID: 1251901
Report Number(s):
SAND--2013-10363J; PII: S1540748914001060
Journal Information:
Proceedings of the Combustion Institute, Journal Name: Proceedings of the Combustion Institute Journal Issue: 1 Vol. 35; ISSN 1540-7489
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (4)

Experimental and Kinetic Modeling Study of C 2 H 2 Oxidation at High Pressure: EXPERIMENTAL AND KINETIC MODELING STUDY OF C 2 H 2 OXIDATION AT HIGH PRESSURE journal August 2016
Interactive molecular dynamics in virtual reality from quantum chemistry to drug binding: An open-source multi-person framework journal June 2019
Interactive molecular dynamics in virtual reality from quantum chemistry to drug binding: An open-source multi-person framework text January 2019
Estimation of rate coefficients and branching ratios for gas-phase reactions of OH with aliphatic organic compounds for use in automated mechanism construction journal January 2018

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
master equation
pressure dependence
propargyl