Theoretical kinetics of O + C2H4
Abstract
The reaction of atomic oxygen with ethylene is a fundamental oxidation step in combustion and is prototypical of reactions in which oxygen adds to double bonds. For 3O+C2H4 and for this class of reactions generally, decomposition of the initial adduct via spin-allowed reaction channels on the triplet surface competes with intersystem crossing (ISC) and a set of spin-forbidden reaction channels on the ground-state singlet surface. The two surfaces share some bimolecular products but feature different intermediates, pathways, and transition states. In addition, the overall product branching is therefore a sensitive function of the ISC rate. The 3O+C2H4 reaction has been extensively studied, but previous experimental work has not provided detailed branching information at elevated temperatures, while previous theoretical studies have employed empirical treatments of ISC. Here we predict the kinetics of 3O+C2H4 using an ab initio transition state theory based master equation (AITSTME) approach that includes an a priori description of ISC. Specifically, the ISC rate is calculated using Landau–Zener statistical theory, consideration of the four lowest-energy electronic states, and a direct classical trajectory study of the product branching immediately after ISC. The present theoretical results are largely in good agreement with existing low-temperature experimental kinetics and molecular beam studies.more »
- 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-NM), Albuquerque, NM (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1323886
- Alternate Identifier(s):
- OSTI ID: 1412967
- Report Number(s):
- SAND-2016-4959J
Journal ID: ISSN 1540-7489; 640738
- Grant/Contract Number:
- AC04-94AL85000; AC04-94-AL85000; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Proceedings of the Combustion Institute
- Additional Journal Information:
- Journal Name: Proceedings of the Combustion Institute; Journal ID: ISSN 1540-7489
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Cvetanović; non-adiabatic transition state theory; RRKM
Citation Formats
Li, Xiaohu, Jasper, Ahren W., Zádor, Judit, Miller, James A., and Klippenstein, Stephen J. Theoretical kinetics of O + C2H4. United States: N. p., 2016.
Web. doi:10.1016/j.proci.2016.06.053.
Li, Xiaohu, Jasper, Ahren W., Zádor, Judit, Miller, James A., & Klippenstein, Stephen J. Theoretical kinetics of O + C2H4. United States. https://doi.org/10.1016/j.proci.2016.06.053
Li, Xiaohu, Jasper, Ahren W., Zádor, Judit, Miller, James A., and Klippenstein, Stephen J. Wed .
"Theoretical kinetics of O + C2H4". United States. https://doi.org/10.1016/j.proci.2016.06.053. https://www.osti.gov/servlets/purl/1323886.
@article{osti_1323886,
title = {Theoretical kinetics of O + C2H4},
author = {Li, Xiaohu and Jasper, Ahren W. and Zádor, Judit and Miller, James A. and Klippenstein, Stephen J.},
abstractNote = {The reaction of atomic oxygen with ethylene is a fundamental oxidation step in combustion and is prototypical of reactions in which oxygen adds to double bonds. For 3O+C2H4 and for this class of reactions generally, decomposition of the initial adduct via spin-allowed reaction channels on the triplet surface competes with intersystem crossing (ISC) and a set of spin-forbidden reaction channels on the ground-state singlet surface. The two surfaces share some bimolecular products but feature different intermediates, pathways, and transition states. In addition, the overall product branching is therefore a sensitive function of the ISC rate. The 3O+C2H4 reaction has been extensively studied, but previous experimental work has not provided detailed branching information at elevated temperatures, while previous theoretical studies have employed empirical treatments of ISC. Here we predict the kinetics of 3O+C2H4 using an ab initio transition state theory based master equation (AITSTME) approach that includes an a priori description of ISC. Specifically, the ISC rate is calculated using Landau–Zener statistical theory, consideration of the four lowest-energy electronic states, and a direct classical trajectory study of the product branching immediately after ISC. The present theoretical results are largely in good agreement with existing low-temperature experimental kinetics and molecular beam studies. Good agreement is also found with past theoretical work, with the notable exception of the predicted product branching at elevated temperatures. Above ~1000 K, we predict CH2CHO+H and CH2+CH2O as the major products, which differs from the room temperature preference for CH3+HCO (which is assumed to remain at higher temperatures in some models) and from the prediction of a previous detailed master equation study.},
doi = {10.1016/j.proci.2016.06.053},
journal = {Proceedings of the Combustion Institute},
number = ,
volume = ,
place = {United States},
year = {Wed Jun 01 00:00:00 EDT 2016},
month = {Wed Jun 01 00:00:00 EDT 2016}
}
Web of Science
Works referenced in this record:
Formation of nitric oxide in premixed hydrocarbon flames
journal, January 1971
- Fenimore, C. P.
- Symposium (International) on Combustion, Vol. 13, Issue 1
Mechanism and modeling of nitrogen chemistry in combustion
journal, January 1989
- Miller, James A.; Bowman, Craig T.
- Progress in Energy and Combustion Science, Vol. 15, Issue 4
Unravelling combustion mechanisms through a quantitative understanding of elementary reactions
journal, January 2005
- Miller, James A.; Pilling, Michael J.; Troe, Jürgen
- Proceedings of the Combustion Institute, Vol. 30, Issue 1
Kinetics of CH + N 2 Revisited with Multireference Methods
journal, January 2008
- Harding, Lawrence B.; Klippenstein, Stephen J.; Miller, James A.
- The Journal of Physical Chemistry A, Vol. 112, Issue 3
The spin-conserved reaction CH+N2→H+NCN: A major pathway to prompt no studied by quantum/statistical theory calculations and kinetic modeling of rate constant
journal, January 2000
- Moskaleva, L. V.; Lin, M. C.
- Proceedings of the Combustion Institute, Vol. 28, Issue 2
Evaluated Chemical Kinetic Data for the Reactions of Atomic Oxygen O( 3 P) with Unsaturated Hydrocarbons
journal, April 1987
- Cvetanović, R. J.
- Journal of Physical and Chemical Reference Data, Vol. 16, Issue 2
Evaluated Kinetic Data for Combustion Modeling: Supplement II
journal, September 2005
- Baulch, D. L.; Bowman, C. T.; Cobos, C. J.
- Journal of Physical and Chemical Reference Data, Vol. 34, Issue 3
Product branching fractions for the reaction of O(3P) with ethene
journal, January 2009
- Miyoshi, Akira; Yoshida, Jun-ichi; Shiki, Naoya
- Physical Chemistry Chemical Physics, Vol. 11, Issue 33
Branching ratio for the hydrogen atom product channel in the reaction of ground-state atomic oxygen with ethylene
journal, January 1986
- Smalley, John F.; Nesbitt, Fred L.; Klemm, R. Bruce
- The Journal of Physical Chemistry, Vol. 90, Issue 3
Potential Energy Surfaces, Product Distributions and Thermal Rate Coefficients of the Reaction of O( 3 P) with C 2 H 4 (X 1 A g ): A Comprehensive Theoretical Study
journal, August 2005
- Nguyen, Thanh Lam; Vereecken, Luc; Hou, Xin Juan
- The Journal of Physical Chemistry A, Vol. 109, Issue 33
Primary products of the reaction between O(3P)-atoms and C2H4 studied with ESR- and LMR-detection
journal, January 1989
- Bley, U.; Dransfeld, P.; Himme, B.
- Symposium (International) on Combustion, Vol. 22, Issue 1
Crossed molecular beam study of the reaction O( 3 P )+C 2 H 4
journal, December 1989
- Schmoltner, A. M.; Chu, P. M.; Brudzynski, R. J.
- The Journal of Chemical Physics, Vol. 91, Issue 11
Photodissociating methyl vinyl ether to calibrate O+ethylene product branching and to test propensity rules for product channel electronic accessibility
journal, July 2001
- Morton, M. L.; Szpunar, D. E.; Butler, L. J.
- The Journal of Chemical Physics, Vol. 115, Issue 1
Dynamics of the O(3P) + C2H4 Reaction: Identification of Five Primary Product Channels (Vinoxy, Acetyl, Methyl, Methylene, and Ketene) and Branching Ratios by the Crossed Molecular Beam Technique with Soft Electron Ionization
journal, March 2005
- Casavecchia, Piergiorgio; Capozza, Giovanni; Segoloni, Enrico
- The Journal of Physical Chemistry A, Vol. 109, Issue 16
Experimental and theoretical studies of the O( 3 P) + C 2 H 4 reaction dynamics: Collision energy dependence of branching ratios and extent of intersystem crossing
journal, December 2012
- Fu, Bina; Han, Yong-Chang; Bowman, Joel M.
- The Journal of Chemical Physics, Vol. 137, Issue 22
Crossed Molecular Beams and Quasiclassical Trajectory Surface Hopping Studies of the Multichannel Nonadiabatic O( 3 P) + Ethylene Reaction at High Collision Energy
journal, October 2015
- Balucani, Nadia; Leonori, Francesca; Casavecchia, Piergiorgio
- The Journal of Physical Chemistry A, Vol. 119, Issue 50
Molecular dynamics with electronic transitions
journal, July 1990
- Tully, John C.
- The Journal of Chemical Physics, Vol. 93, Issue 2
Introductory lecture: Nonadiabatic effects in chemical dynamics
journal, January 2004
- Jasper, Ahren W.; Zhu, Chaoyuan; Nangia, Shikha
- Faraday Discussions, Vol. 127
Trajectory Surface Hopping Study of the O( 3 P) + Ethylene Reaction Dynamics
journal, December 2007
- Hu, Wenfang; Lendvay, György; Maiti, Biswajit
- The Journal of Physical Chemistry A, Vol. 112, Issue 10
Oxidation of Ethylene—Air Mixtures at Elevated Pressures, Part 2: Chemical Kinetics
journal, May 2014
- Kopp, Madeleine M.; Petersen, Eric L.; Metcalfe, Wayne K.
- Journal of Propulsion and Power, Vol. 30, Issue 3
Oxidation of Ethylene–Air Mixtures at Elevated Pressures, Part 1: Experimental Results
journal, May 2014
- Kopp, Madeleine M.; Donato, Nicole S.; Petersen, Eric L.
- Journal of Propulsion and Power, Vol. 30, Issue 3
O + C2H4 potential energy surface: excited states and biradicals at the multireference level
journal, February 2012
- West, Aaron C.; Lynch, Joseph D.; Sellner, Bernhard
- Theoretical Chemistry Accounts, Vol. 131, Issue 3
Basis set convergence in second-row compounds. The importance of core polarization functions
journal, January 1998
- Martin, Jan M. L.; Uzan, Olivier
- Chemical Physics Letters, Vol. 282, Issue 1
Gaussian basis sets for use in correlated molecular calculations. V. Core‐valence basis sets for boron through neon
journal, September 1995
- Woon, David E.; Dunning, Thom H.
- The Journal of Chemical Physics, Vol. 103, Issue 11
Higher excitations in coupled-cluster theory
journal, August 2001
- Kállay, Mihály; Surján, Péter R.
- The Journal of Chemical Physics, Vol. 115, Issue 7
Ab Initio Computations and Active Thermochemical Tables Hand in Hand: Heats of Formation of Core Combustion Species
journal, August 2017
- Klippenstein, Stephen J.; Harding, Lawrence B.; Ruscic, Branko
- The Journal of Physical Chemistry A, Vol. 121, Issue 35
Transition State Theory for Multichannel Addition Reactions: Multifaceted Dividing Surfaces
journal, November 2003
- Georgievskii, Yuri; Klippenstein, Stephen J.
- The Journal of Physical Chemistry A, Vol. 107, Issue 46
Roaming Radical Kinetics in the Decomposition of Acetaldehyde
journal, January 2010
- Harding, Lawrence B.; Georgievskii, Yuri; Klippenstein, Stephen J.
- The Journal of Physical Chemistry A, Vol. 114, Issue 2
The spin-forbidden reaction CH(2Π)+N2→HCN+N(4S) revisited. II. Nonadiabatic transition state theory and application
journal, May 1999
- Cui, Qiang; Morokuma, Keiji; Bowman, Joel M.
- The Journal of Chemical Physics, Vol. 110, Issue 19
Understanding the kinetics of spin-forbidden chemical reactions
journal, January 2007
- Harvey, Jeremy N.
- Phys. Chem. Chem. Phys., Vol. 9, Issue 3
Multidimensional Effects in Nonadiabatic Statistical Theories of Spin-Forbidden Kinetics: A Case Study of 3 O + CO → CO 2
journal, February 2015
- Jasper, Ahren W.
- The Journal of Physical Chemistry A, Vol. 119, Issue 28
n -electron valence state perturbation theory: A spinless formulation and an efficient implementation of the strongly contracted and of the partially contracted variants
journal, November 2002
- Angeli, Celestino; Cimiraglia, Renzo; Malrieu, Jean-Paul
- The Journal of Chemical Physics, Vol. 117, Issue 20
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
Determination of branching ratios for the reaction of oxygen atoms with ethylene
journal, March 1974
- Pruss, Frank J.; Slagle, Irene R.; Gutman, David
- The Journal of Physical Chemistry, Vol. 78, Issue 7
Works referencing / citing this record:
Molecular beam studies of elementary reactions relevant in plasma/combustion chemistry: O(3P) + unsaturated hydrocarbons
journal, July 2019
- Caracciolo, Adriana; Vanuzzo, Gianmarco; Recio, Pedro
- Rendiconti Lincei. Scienze Fisiche e Naturali, Vol. 30, Issue 3