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Title: Ephemeral collision complexes mediate chemically termolecular transformations that affect system chemistry [Ephemeral collision complexes induce chemically termolecular transformations that affect global chemistry]

Abstract

Termolecular association reactions involve ephemeral collision complexes—formed from the collision of two molecules—that collide with a third and chemically inert ‘bath gas’ molecule that simply transfers energy to/from the complex. These collision complexes are generally not thought to react chemically on collision with a third molecule in the gas-phase systems of combustion and planetary atmospheres. Such ‘chemically termolecular’ reactions, in which all three molecules are involved in bond making and/or breaking, were hypothesized long ago in studies establishing radical chain branching mechanisms, but were later concluded to be unimportant. Here, with data from ab initio master equation and kinetic-transport simulations, we reveal that reactions of H+O2 collision complexes with other radicals constitute major kinetic pathways under common combustion situations. These reactions are also found to influence flame propagation speeds, a common measure of global reactivity. As a result, analogous chemically termolecular reactions mediated by ephemeral collision complexes are probably of significance in various combustion and planetary environments.

Authors:
ORCiD logo [1];  [2]
  1. Columbia Univ., New York, NY (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1400399
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Chemistry
Additional Journal Information:
Journal Volume: 2017; Journal ID: ISSN 1755-4330
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Burke, Michael P., and Klippenstein, Stephen J. Ephemeral collision complexes mediate chemically termolecular transformations that affect system chemistry [Ephemeral collision complexes induce chemically termolecular transformations that affect global chemistry]. United States: N. p., 2017. Web. doi:10.1038/nchem.2842.
Burke, Michael P., & Klippenstein, Stephen J. Ephemeral collision complexes mediate chemically termolecular transformations that affect system chemistry [Ephemeral collision complexes induce chemically termolecular transformations that affect global chemistry]. United States. doi:10.1038/nchem.2842.
Burke, Michael P., and Klippenstein, Stephen J. Mon . "Ephemeral collision complexes mediate chemically termolecular transformations that affect system chemistry [Ephemeral collision complexes induce chemically termolecular transformations that affect global chemistry]". United States. doi:10.1038/nchem.2842. https://www.osti.gov/servlets/purl/1400399.
@article{osti_1400399,
title = {Ephemeral collision complexes mediate chemically termolecular transformations that affect system chemistry [Ephemeral collision complexes induce chemically termolecular transformations that affect global chemistry]},
author = {Burke, Michael P. and Klippenstein, Stephen J.},
abstractNote = {Termolecular association reactions involve ephemeral collision complexes—formed from the collision of two molecules—that collide with a third and chemically inert ‘bath gas’ molecule that simply transfers energy to/from the complex. These collision complexes are generally not thought to react chemically on collision with a third molecule in the gas-phase systems of combustion and planetary atmospheres. Such ‘chemically termolecular’ reactions, in which all three molecules are involved in bond making and/or breaking, were hypothesized long ago in studies establishing radical chain branching mechanisms, but were later concluded to be unimportant. Here, with data from ab initio master equation and kinetic-transport simulations, we reveal that reactions of H+O2 collision complexes with other radicals constitute major kinetic pathways under common combustion situations. These reactions are also found to influence flame propagation speeds, a common measure of global reactivity. As a result, analogous chemically termolecular reactions mediated by ephemeral collision complexes are probably of significance in various combustion and planetary environments.},
doi = {10.1038/nchem.2842},
journal = {Nature Chemistry},
number = ,
volume = 2017,
place = {United States},
year = {2017},
month = {8}
}

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Works referenced in this record:

Master equation simulations of competing unimolecular and bimolecular reactions: application to OH production in the reaction of acetyl radical with O2
journal, January 2007

  • Maranzana, Andrea; Barker, John R.; Tonachini, Glauco
  • Physical Chemistry Chemical Physics, Vol. 9, Issue 31
  • DOI: 10.1039/b705116f

Radiation and chemistry
journal, January 1922


First-Principles Theory for the H + CH4 -> H2 + CH3 Reaction
journal, December 2004


An extended mechanism for chemical activation systems
journal, September 1991

  • Olzmann, M.; Gebhardt, J.; Scherzer, K.
  • International Journal of Chemical Kinetics, Vol. 23, Issue 9
  • DOI: 10.1002/kin.550230909

An experimental and detailed chemical kinetic modeling study of hydrogen and syngas mixture oxidation at elevated pressures
journal, June 2013


A VTST Study of the H + O 3 and O + HO 2 Reactions Using a Six-dimensional DMBE Potential Energy Surface for Ground State HO 3
journal, April 2002

  • Fernández-Ramos, A.; Varandas, A. J. C.
  • The Journal of Physical Chemistry A, Vol. 106, Issue 16
  • DOI: 10.1021/jp014120k

Do Vibrational Excitations of CHD3 Preferentially Promote Reactivity Toward the Chlorine Atom?
journal, June 2007


Spectroscopic observation of resonances in the F + H2 reaction
journal, July 2015


Pressure dependent low temperature kinetics for CN + CH 3 CN: competition between chemical reaction and van der Waals complex formation
journal, January 2016

  • Sleiman, Chantal; González, Sergio; Klippenstein, Stephen J.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 22
  • DOI: 10.1039/C6CP01982J

M ASTER E QUATION M ODELS FOR C HEMICAL R EACTIONS OF I MPORTANCE IN C OMBUSTION
journal, October 2003


Dynamics of the Reaction of Methane with Chlorine Atom on an Accurate Potential Energy Surface
journal, October 2011


Rapid Association Reactions at low Pressure: Impact on the Formation of Hydrocarbons on Titan
journal, December 2011


Towards a quantitative understanding of the role of non-Boltzmann reactant distributions in low temperature oxidation
journal, January 2015

  • Burke, Michael P.; Goldsmith, C. Franklin; Georgievskii, Yuri
  • Proceedings of the Combustion Institute, Vol. 35, Issue 1
  • DOI: 10.1016/j.proci.2014.05.118

A Chemical Kinetics Network for Lightning and life in Planetary Atmospheres
journal, May 2016


On the Theory of Unimolecular Reactions
journal, November 1926

  • Hinshelwood, C. N.
  • Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 113, Issue 763
  • DOI: 10.1098/rspa.1926.0149

Laser Control of Chemical Reactions
journal, March 1998


Discussion on “the radiation theory of chemical action”
journal, January 1922

  • Lindemann, F. A.; Arrhenius, Svante; Langmuir, Irving
  • Trans. Faraday Soc., Vol. 17, Issue 0
  • DOI: 10.1039/TF9221700598

Interception of Excited Vibrational Quantum States by O2 in Atmospheric Association Reactions
journal, August 2012


Transition-State Spectroscopy of Partial Wave Resonances in the F + HD Reaction
journal, March 2010


The first limit of the hydrogen + oxygen reaction in potassium chloride-coated vessels
journal, January 1956


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
  • DOI: 10.1021/jp4060704

Master Equation Analysis of Pressure-Dependent Atmospheric Reactions
journal, December 2003

  • Barker, John R.; Golden, David M.
  • Chemical Reviews, Vol. 103, Issue 12
  • DOI: 10.1021/cr020655d

Comprehensive H2/O2 kinetic model for high-pressure combustion
journal, December 2011

  • Burke, Michael P.; Chaos, Marcos; Ju, Yiguang
  • International Journal of Chemical Kinetics, Vol. 44, Issue 7
  • DOI: 10.1002/kin.20603

A quantitative explanation for the apparent anomalous temperature dependence of OH+HO2=H2O+O2 through multi-scale modeling
journal, January 2013

  • Burke, Michael P.; Klippenstein, Stephen J.; Harding, Lawrence B.
  • Proceedings of the Combustion Institute, Vol. 34, Issue 1
  • DOI: 10.1016/j.proci.2012.05.041

CII.—The interaction of nitric oxide and hydrogen and the molecular statistics of termolecular gaseous reactions
journal, January 1926

  • Hinshelwood, Cyril Norman; Green, Thomas Edward
  • J. Chem. Soc., Vol. 129, Issue 0
  • DOI: 10.1039/JR9262900730

Predictive a priori pressure-dependent kinetics
journal, December 2014


Shock Synthesis of Amino Acids in Simulated Primitive Environments
journal, April 1970


Morphology and burning rates of expanding spherical flames in H2/O2/inert mixtures up to 60 atmospheres
journal, January 2000


Formation of NH3 and CH2NH in Titan's upper atmosphere
journal, January 2010

  • Yelle, Roger V.; Vuitton, V.; Lavvas, P.
  • Faraday Discussions, Vol. 147
  • DOI: 10.1039/c004787m

On the Interpretation of Halogen Atom Recombination Rates 1
journal, October 1958

  • Bunker, Don L.; Davidson, Norman
  • Journal of the American Chemical Society, Vol. 80, Issue 19
  • DOI: 10.1021/ja01552a024

On the Chaperon Mechanism:  Application to ClO + ClO (+N 2 ) → ClOOCl (+N 2 )
journal, September 2007

  • Liu, Jingyao; Barker, John R.
  • The Journal of Physical Chemistry A, Vol. 111, Issue 35
  • DOI: 10.1021/jp072978p

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
  • DOI: 10.1021/jp062693x

The Temperature and Pressure Dependence of the Reactions H + O 2 (+M) → HO 2 (+M) and H + OH (+M) → H 2 O (+M)
journal, June 2008

  • Sellevåg, Stig R.; Georgievskii, Yuri; Miller, James A.
  • The Journal of Physical Chemistry A, Vol. 112, Issue 23
  • DOI: 10.1021/jp711800z