Adventures on the C3H5O potential energy surface: OH+propyne, OH+allene and related reactions
Abstract
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.
- Authors:
-
- Sandia National Lab. (SNL-CA), Livermore, CA (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-CA), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1122136
- Alternate Identifier(s):
- OSTI ID: 1251901
- Report Number(s):
- SAND-2013-10363J
Journal ID: ISSN 1540-7489; PII: S1540748914001060
- Grant/Contract Number:
- AC04-94AL85000
- Resource 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
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; pressure dependence; propargyl; master equation
Citation Formats
Zádor, Judit, and Miller, James A. Adventures on the C3H5O potential energy surface: OH+propyne, OH+allene and related reactions. United States: N. p., 2014.
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. https://doi.org/10.1016/j.proci.2014.05.103
Zádor, Judit, and Miller, James A. Wed .
"Adventures on the C3H5O potential energy surface: OH+propyne, OH+allene and related reactions". United States. https://doi.org/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 = {Wed Jun 25 00:00:00 EDT 2014},
month = {Wed Jun 25 00:00:00 EDT 2014}
}
Web of Science
Works referenced in this record:
Photoionization of the Lower Aliphatic Alcohols with Mass Analysis
journal, June 1968
- Refaey, Kamel M. A.; Chupka, William A.
- The Journal of Chemical Physics, Vol. 48, Issue 11
The Recombination of Propargyl Radicals: Solving the Master Equation
journal, August 2001
- Miller, James A.; Klippenstein, Stephen J.
- The Journal of Physical Chemistry A, Vol. 105, Issue 30
Isomer-specific combustion chemistry in allene and propyne flames
journal, November 2009
- Hansen, Nils; Miller, James A.; Westmoreland, Phillip R.
- Combustion and Flame, Vol. 156, Issue 11
Atom-radical reaction dynamics of O(3P)+C3H5→C3H4+OH: Nascent rovibrational state distributions of product OH
journal, August 2002
- Park, Jong-Ho; Lee, Hohjai; Kwon, Han-Cheol
- The Journal of Chemical Physics, Vol. 117, Issue 5
A theoretical study of the reaction of O(3P) with an allyl radical C3H5
journal, November 2003
- Park, Jong-Ho; Lee, Hohjai; Choi, Jong-Ho
- The Journal of Chemical Physics, Vol. 119, Issue 17
Crossed beam investigations of the reaction dynamics of O(3P) with allyl radical, C3H5
journal, February 2002
- Kwon, Han-Cheol; Park, Jong-Ho; Lee, Hohjai
- The Journal of Chemical Physics, Vol. 116, Issue 7
Photofragment imaging study of the CH2CCH2OH radical intermediate of the OH+allene reaction
journal, October 2007
- Raman, Arjun S.; Justine Bell, M.; Lau, Kai-Chung
- The Journal of Chemical Physics, Vol. 127, Issue 15
Primary photodissociation pathways of epichlorohydrin and analysis of the C–C bond fission channels from an O(P3)+allyl radical intermediate
journal, September 2010
- FitzPatrick, Benjamin L.; Alligood, Bridget W.; Butler, Laurie J.
- The Journal of Chemical Physics, Vol. 133, Issue 9
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
- FitzPatrick, Benjamin
- The Journal of Physical Chemistry A, Vol. 115, Issue 9
Gas-Phase Kinetics of the Hydroxyl Radical Reaction with Allene: Absolute Rate Measurements at Low Temperature, Product Determinations, and Calculations
journal, November 2012
- Daranlot, Julien; Hickson, Kevin M.; Loison, Jean-Christophe
- The Journal of Physical Chemistry A, Vol. 116, Issue 45
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
- Liu, Andong; Mulac, William A.; Jonah, Charles D.
- The Journal of Physical Chemistry, Vol. 92, Issue 1
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
- Atkinson, Roger; Aschmann, Sara M.
- International Journal of Chemical Kinetics, Vol. 16, Issue 10
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
- Atkinson, Roger; Aschmann, Sara M.
- International Journal of Chemical Kinetics, Vol. 17, Issue 1
Absolute determinations of the kinetics and temperature dependences of the reactions of OH with a series of alkynes
journal, January 1987
- Boodaghians, Razmik B.; Hall, Ian W.; Toby, Frina S.
- Journal of the Chemical Society, Faraday Transactions 2, Vol. 83, Issue 11
Pulsed Laval nozzle study of the kinetics of OH with unsaturated hydrocarbons at very low temperatures
journal, January 2008
- Taylor, Sally E.; Goddard, Andrew; Blitz, Mark A.
- Phys. Chem. Chem. Phys., Vol. 10, Issue 3
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
- Hatakeyama, Shiro; Washida, Nobuaki; Akimoto, Hajime
- The Journal of Physical Chemistry, Vol. 90, Issue 1
Kinetics of the reaction of hydroxyl radicals with ethylene and with C3 hydrocarbons
journal, January 1973
- Bradley, John N.; Hack, W.; Hoyermann, K.
- Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 69, Issue 0
Ab initio total atomization energies of small molecules — towards the basis set limit
journal, September 1996
- Martin, Jan M. L.
- Chemical Physics Letters, Vol. 259, Issue 5-6
Extended benchmark studies of coupled cluster theory through triple excitations
journal, August 2001
- Feller, David; Dixon, David A.
- The Journal of Chemical Physics, Vol. 115, Issue 8
Simplified CCSD(T)-F12 methods: Theory and benchmarks
journal, February 2009
- Knizia, Gerald; Adler, Thomas B.; Werner, Hans-Joachim
- The Journal of Chemical Physics, Vol. 130, Issue 5
The reaction between propene and hydroxyl
journal, January 2009
- Zádor, Judit; Jasper, Ahren W.; Miller, James A.
- Physical Chemistry Chemical Physics, Vol. 11, Issue 46
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
- Greenwald, Erin E.; North, Simon W.; Georgievskii, Yuri
- The Journal of Physical Chemistry A, Vol. 109, Issue 27
From the Multiple-Well Master Equation to Phenomenological Rate Coefficients: Reactions on a C 3 H 4 Potential Energy Surface
journal, April 2003
- Miller, James A.; Klippenstein, Stephen J.
- The Journal of Physical Chemistry A, Vol. 107, Issue 15
Master Equation Methods in Gas Phase Chemical Kinetics
journal, September 2006
- Miller, James A.; Klippenstein, Stephen J.
- The Journal of Physical Chemistry A, Vol. 110, Issue 36
From the Time-Dependent, Multiple-Well Master Equation to Phenomenological Rate Coefficients
journal, October 2002
- Klippenstein, Stephen J.; Miller, James A.
- The Journal of Physical Chemistry A, Vol. 106, Issue 40
Reformulation and Solution of the Master Equation for Multiple-Well Chemical Reactions
journal, May 2013
- Georgievskii, Yuri; Miller, James A.; Burke, Michael P.
- The Journal of Physical Chemistry A, Vol. 117, Issue 46
Energy Levels and Thermodynamic Functions for Molecules with Internal Rotation I. Rigid Frame with Attached Tops
journal, July 1942
- Pitzer, Kenneth S.; Gwinn, William D.
- The Journal of Chemical Physics, Vol. 10, Issue 7
Unimolecular dissociation of hydroxypropyl and propoxy radicals
journal, January 2013
- Zádor, Judit; Miller, James A.
- Proceedings of the Combustion Institute, Vol. 34, Issue 1
Theoretical rate coefficients for allyl+HO2 and allyloxy decomposition
journal, January 2011
- Goldsmith, C. Franklin; Klippenstein, Stephen J.; Green, William H.
- Proceedings of the Combustion Institute, Vol. 33, Issue 1
Competing Channels in the Propene + OH Reaction: Experiment and Validated Modeling over a Broad Temperature and Pressure Range
journal, November 2011
- Kappler, Claudia; Zádor, Judit; Welz, Oliver
- Zeitschrift für Physikalische Chemie, Vol. 225, Issue 11-12
Absolute photoionization cross-sections of some combustion intermediates
journal, January 2012
- Yang, Bin; Wang, Juan; Cool, Terrill A.
- International Journal of Mass Spectrometry, Vol. 309
Shock-tube and modeling study of acetone pyrolysis and oxidation
journal, August 2000
- Sato, Kazutaka; Hidaka, Yoshiaki
- Combustion and Flame, Vol. 122, Issue 3
Addition of ethyl radicals to carbon monoxide. Kinetic and thermochemical properties of the propionyl radical
journal, September 1973
- Watkins, K. W.; Thompson, William W.
- International Journal of Chemical Kinetics, Vol. 5, Issue 5
The kinetics of hydrogen abstraction by difluoroamino-radicals, from propionaldehyde, and n- and iso-butyraldehyde, and their acyl radical decompositions
journal, January 1970
- Cadman, P.; Dodwell, C.; Trotman-Dickenson, A. F.
- Journal of the Chemical Society A: Inorganic, Physical, Theoretical
Kinetics and pressure dependence of the decomposition of the propionyl radical
journal, January 1967
- Kerr, J. A.; Lloyd, A. C.
- Transactions of the Faraday Society, Vol. 63
Rate constants for the reactions of O3 and OH radicals with a series of alkynes
journal, March 1984
- Atkinson, Roger; Aschmann, Sara M.
- International Journal of Chemical Kinetics, Vol. 16, Issue 3
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
- Atkinson, R.; Perry, R. A.; Pitts, J. N.
- The Journal of Chemical Physics, Vol. 67, Issue 7
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
- Ohta, Tomohiro
- The Journal of Physical Chemistry, Vol. 87, Issue 7
Works referencing / citing this record:
Interactive molecular dynamics in virtual reality from quantum chemistry to drug binding: An open-source multi-person framework
journal, June 2019
- O’Connor, Michael B.; Bennie, Simon J.; Deeks, Helen M.
- The Journal of Chemical Physics, Vol. 150, Issue 22
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
- Jenkin, Michael E.; Valorso, Richard; Aumont, Bernard
- Atmospheric Chemistry and Physics, Vol. 18, Issue 13
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
- Gimenez-Lopez, Jorge; Rasmussen, Christian Tihic; Hashemi, Hamid
- International Journal of Chemical Kinetics, Vol. 48, Issue 11
Interactive molecular dynamics in virtual reality from quantum chemistry to drug binding: An open-source multi-person framework
text, January 2019
- O'Connor, Michael; Bennie, Simon J.; Deeks, Helen M.
- arXiv