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

Journal Article · · Proceedings of the Combustion Institute
ORCiD logo [1];  [2]
  1. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
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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 Lab. (SNL-CA), Livermore, CA (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
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, Vol. 35, Issue 1; ISSN 1540-7489
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 31 works
Citation information provided by
Web of Science

References (38)

Photoionization of the Lower Aliphatic Alcohols with Mass Analysis journal June 1968
The Recombination of Propargyl Radicals:  Solving the Master Equation journal August 2001
Isomer-specific combustion chemistry in allene and propyne flames journal November 2009
Atom-radical reaction dynamics of O(3P)+C3H5→C3H4+OH: Nascent rovibrational state distributions of product OH journal August 2002
A theoretical study of the reaction of O(3P) with an allyl radical C3H5 journal November 2003
Crossed beam investigations of the reaction dynamics of O(3P) with allyl radical, C3H5 journal February 2002
Photofragment imaging study of the CH2CCH2OH radical intermediate of the OH+allene reaction journal October 2007
Primary photodissociation pathways of epichlorohydrin and analysis of the C–C bond fission channels from an O(P3)+allyl radical intermediate journal September 2010
Theoretical Study of Isomerization and Dissociation Transition States of C 3 H 5 O Radical Isomers: Ab Initio Characterization of the Critical Points and Statistical Transition-State Theory Modeling of the Dynamics journal March 2011
Gas-Phase Kinetics of the Hydroxyl Radical Reaction with Allene: Absolute Rate Measurements at Low Temperature, Product Determinations, and Calculations journal November 2012
Rate constants for the gas-phase reactions of hydroxyl radicals with 1,3-butadiene and allene at 1 atm in argon and over the temperature range 305-1173 K journal January 1988
Rate constants for the reaction of OH radicals with a series of alkenes and dialkenes at 295 ± 1 K: RATE CONSTANTS FOR REACTION OF OH RADICALS journal October 1984
Kinetics of the gas phase reaction of Cl atoms with a series of organics at 296 ± 2 K and atmospheric pressure: KINETICS OF THE GAS PHASE REACTION OF Cl ATOMS journal January 1985
Absolute determinations of the kinetics and temperature dependences of the reactions of OH with a series of alkynes journal January 1987
Pulsed Laval nozzle study of the kinetics of OH with unsaturated hydrocarbons at very low temperatures journal January 2008
Rate constants and mechanisms for the reaction of hydroxyl (OD) radicals with acetylene, propyne, and 2-butyne in air at 297 .+-. 2 K journal January 1986
Kinetics of the reaction of hydroxyl radicals with ethylene and with C3 hydrocarbons
  • Bradley, John N.; Hack, W.; Hoyermann, K.
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 69, Issue 0 https://doi.org/10.1039/f19736901889
journal January 1973
Ab initio total atomization energies of small molecules — towards the basis set limit journal September 1996
Extended benchmark studies of coupled cluster theory through triple excitations journal August 2001
Simplified CCSD(T)-F12 methods: Theory and benchmarks journal February 2009
The reaction between propene and hydroxyl journal January 2009
A Two Transition State Model for Radical−Molecule Reactions:  A Case Study of the Addition of OH to C 2 H 4 journal July 2005
From the Multiple-Well Master Equation to Phenomenological Rate Coefficients:  Reactions on a C 3 H 4 Potential Energy Surface journal April 2003
Master Equation Methods in Gas Phase Chemical Kinetics journal September 2006
From the Time-Dependent, Multiple-Well Master Equation to Phenomenological Rate Coefficients journal October 2002
Reformulation and Solution of the Master Equation for Multiple-Well Chemical Reactions journal May 2013
Energy Levels and Thermodynamic Functions for Molecules with Internal Rotation I. Rigid Frame with Attached Tops journal July 1942
Unimolecular dissociation of hydroxypropyl and propoxy radicals journal January 2013
Theoretical rate coefficients for allyl+HO2 and allyloxy decomposition journal January 2011
Competing Channels in the Propene + OH Reaction: Experiment and Validated Modeling over a Broad Temperature and Pressure Range journal November 2011
Absolute photoionization cross-sections of some combustion intermediates journal January 2012
Shock-tube and modeling study of acetone pyrolysis and oxidation journal August 2000
Addition of ethyl radicals to carbon monoxide. Kinetic and thermochemical properties of the propionyl radical journal September 1973
The kinetics of hydrogen abstraction by difluoroamino-radicals, from propionaldehyde, and n- and iso-butyraldehyde, and their acyl radical decompositions journal January 1970
Kinetics and pressure dependence of the decomposition of the propionyl radical journal January 1967
Rate constants for the reactions of O3 and OH radicals with a series of alkynes journal March 1984
Absolute rate constants for the reaction of OH radicals with allene, 1,3‐butadiene, and 3‐methyl‐1‐butene over the temperature range 299–424 °K journal October 1977
Rate constants for reactions of diolefins with hydroxyl radicals in the gas phase. Estimate of the rate constants from those for monoolefins journal March 1983

Cited By (4)

Interactive molecular dynamics in virtual reality from quantum chemistry to drug binding: An open-source multi-person framework journal June 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
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 text January 2019

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Related Subjects

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