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Theoretical kinetics of O + C2H4

Journal Article · · Proceedings of the Combustion Institute
 [1];  [1];  [1];  [2];  [2]
  1. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
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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.
Research Organization:
Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357; AC04-94AL85000
OSTI ID:
1323886
Alternate ID(s):
OSTI ID: 1412967
Report Number(s):
SAND--2016-4959J; 640738
Journal Information:
Proceedings of the Combustion Institute, Journal Name: Proceedings of the Combustion Institute; ISSN 1540-7489
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

References (34)

O + C2H4 potential energy surface: excited states and biradicals at the multireference level journal February 2012
Mechanism and modeling of nitrogen chemistry in combustion journal January 1989
Basis set convergence in second-row compounds. The importance of core polarization functions journal January 1998
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
Formation of nitric oxide in premixed hydrocarbon flames journal January 1971
Primary products of the reaction between O(3P)-atoms and C2H4 studied with ESR- and LMR-detection journal January 1989
Unravelling combustion mechanisms through a quantitative understanding of elementary reactions journal January 2005
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
Ab Initio Computations and Active Thermochemical Tables Hand in Hand: Heats of Formation of Core Combustion Species journal August 2017
Branching ratio for the hydrogen atom product channel in the reaction of ground-state atomic oxygen with ethylene journal January 1986
Determination of branching ratios for the reaction of oxygen atoms with ethylene journal March 1974
Transition State Theory for Multichannel Addition Reactions:  Multifaceted Dividing Surfaces journal November 2003
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
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
Trajectory Surface Hopping Study of the O( 3 P) + Ethylene Reaction Dynamics journal December 2007
Kinetics of CH + N 2 Revisited with Multireference Methods journal January 2008
Reformulation and Solution of the Master Equation for Multiple-Well Chemical Reactions journal May 2013
Multidimensional Effects in Nonadiabatic Statistical Theories of Spin-Forbidden Kinetics: A Case Study of 3 O + CO → CO 2 journal February 2015
Roaming Radical Kinetics in the Decomposition of Acetaldehyde journal January 2010
Understanding the kinetics of spin-forbidden chemical reactions journal January 2007
Introductory lecture: Nonadiabatic effects in chemical dynamics journal January 2004
Product branching fractions for the reaction of O(3P) with ethene journal January 2009
Photodissociating methyl vinyl ether to calibrate O+ethylene product branching and to test propensity rules for product channel electronic accessibility journal July 2001
Higher excitations in coupled-cluster theory journal August 2001
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
Evaluated Kinetic Data for Combustion Modeling: Supplement II journal September 2005
Crossed molecular beam study of the reaction O( 3 P )+C 2 H 4 journal December 1989
Molecular dynamics with electronic transitions journal July 1990
Gaussian basis sets for use in correlated molecular calculations. V. Core‐valence basis sets for boron through neon journal September 1995
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
The spin-forbidden reaction CH(2Π)+N2→HCN+N(4S) revisited. II. Nonadiabatic transition state theory and application journal May 1999
Evaluated Chemical Kinetic Data for the Reactions of Atomic Oxygen O( 3 P) with Unsaturated Hydrocarbons journal April 1987
Oxidation of Ethylene–Air Mixtures at Elevated Pressures, Part 1: Experimental Results journal May 2014
Oxidation of Ethylene—Air Mixtures at Elevated Pressures, Part 2: Chemical Kinetics journal May 2014

Cited By (1)

Molecular beam studies of elementary reactions relevant in plasma/combustion chemistry: O(3P) + unsaturated hydrocarbons journal July 2019

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