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Title: 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 » 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.« less

Authors:
 [1];  [1];  [1];  [2];  [2]
  1. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  2. 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. https://doi.org/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 = {2016},
month = {6}
}

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    Works referencing / citing this record:

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