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Title: The Effect of Alcohol and Carbonyl Functional Groups on the Competition between Unimolecular Decomposition and Isomerization in C 4 and C 5 Alkoxy Radicals: EFFECT OF ALCOHOL AND CARBONYL FUNCTIONAL GROUPS ON C4 AND C5 ALKOXY RADICALS

Authors:
 [1];  [1]
  1. Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge MA 02139
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Combustion Energy Frontier Research Center (CEFRC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1369856
DOE Contract Number:  
SC0001198
Resource Type:
Journal Article
Journal Name:
International Journal of Chemical Kinetics
Additional Journal Information:
Journal Volume: 48; Journal Issue: 9; Related Information: CEFRC partners with Princeton University (lead); Argonne National Laboratory; University of Connecticut; Cornell University; Massachusetts Institute of Technology; University of Minnesota; Sandia National Laboratories; University of Southern California; Stanford University; University of Wisconsin, Madison; Journal ID: ISSN 0538-8066
Country of Publication:
United States
Language:
English

Citation Formats

Dames, Enoch E., and Green, William H. The Effect of Alcohol and Carbonyl Functional Groups on the Competition between Unimolecular Decomposition and Isomerization in C 4 and C 5 Alkoxy Radicals: EFFECT OF ALCOHOL AND CARBONYL FUNCTIONAL GROUPS ON C4 AND C5 ALKOXY RADICALS. United States: N. p., 2016. Web. doi:10.1002/kin.21015.
Dames, Enoch E., & Green, William H. The Effect of Alcohol and Carbonyl Functional Groups on the Competition between Unimolecular Decomposition and Isomerization in C 4 and C 5 Alkoxy Radicals: EFFECT OF ALCOHOL AND CARBONYL FUNCTIONAL GROUPS ON C4 AND C5 ALKOXY RADICALS. United States. doi:10.1002/kin.21015.
Dames, Enoch E., and Green, William H. Tue . "The Effect of Alcohol and Carbonyl Functional Groups on the Competition between Unimolecular Decomposition and Isomerization in C 4 and C 5 Alkoxy Radicals: EFFECT OF ALCOHOL AND CARBONYL FUNCTIONAL GROUPS ON C4 AND C5 ALKOXY RADICALS". United States. doi:10.1002/kin.21015.
@article{osti_1369856,
title = {The Effect of Alcohol and Carbonyl Functional Groups on the Competition between Unimolecular Decomposition and Isomerization in C 4 and C 5 Alkoxy Radicals: EFFECT OF ALCOHOL AND CARBONYL FUNCTIONAL GROUPS ON C4 AND C5 ALKOXY RADICALS},
author = {Dames, Enoch E. and Green, William H.},
abstractNote = {},
doi = {10.1002/kin.21015},
journal = {International Journal of Chemical Kinetics},
issn = {0538-8066},
number = 9,
volume = 48,
place = {United States},
year = {2016},
month = {7}
}

Works referenced in this record:

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
  • DOI: 10.1063/1.3054300

Mechanism of atmospheric photooxidation of organic compounds. Reactions of alkoxy radicals in oxidation of n-butane and simple ketones
journal, May 1981

  • Cox, Richard A.; Patrick, Kenneth F.; Chant, Susan A.
  • Environmental Science & Technology, Vol. 15, Issue 5
  • DOI: 10.1021/es00087a011

Decomposition of substituted alkoxy radicals—part I: a generalized structure–activity relationship for reaction barrier heights
journal, January 2009

  • Vereecken, L.; Peeters, J.
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 40
  • DOI: 10.1039/b909712k

Rate constants for the atmospheric reactions of alkoxy radicals: An updated estimation method
journal, December 2007


Complete falloff curves for the unimolecular decomposition of i-propoxy radicals between 330 and 408 K
journal, January 1999

  • Devolder, P.; Fittschen, Ch; Frenzel, A.
  • Physical Chemistry Chemical Physics, Vol. 1, Issue 4
  • DOI: 10.1039/a808091g

Local explicitly correlated coupled-cluster methods: Efficient removal of the basis set incompleteness and domain errors
journal, June 2009

  • Adler, Thomas B.; Werner, Hans-Joachim
  • The Journal of Chemical Physics, Vol. 130, Issue 24
  • DOI: 10.1063/1.3160675

Intramolecular Hydrogen Migration in Alkylperoxy and Hydroperoxyalkylperoxy Radicals: Accurate Treatment of Hindered Rotors
journal, May 2010

  • Sharma, Sandeep; Raman, Sumathy; Green, William H.
  • The Journal of Physical Chemistry A, Vol. 114, Issue 18
  • DOI: 10.1021/jp9098792

Theoretical studies of unimolecular reactions of C2–C5 alkoxy radicals. Part II. RRKM dynamical calculations
journal, January 2000

  • Somnitz, H.; Zellner, R.
  • Physical Chemistry Chemical Physics, Vol. 2, Issue 9
  • DOI: 10.1039/b000029i

A Generalized Structure-Activity Relationship for the Decomposition of (Substituted) Alkoxy Radicals
journal, May 2004


Development of density functionals for thermochemical kinetics
journal, August 2004

  • Boese, A. Daniel; Martin, Jan M. L.
  • The Journal of Chemical Physics, Vol. 121, Issue 8
  • DOI: 10.1063/1.1774975

Molpro: a general-purpose quantum chemistry program package: Molpro
journal, July 2011

  • Werner, Hans-Joachim; Knowles, Peter J.; Knizia, Gerald
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2
  • DOI: 10.1002/wcms.82

A simple and efficient CCSD(T)-F12 approximation
journal, December 2007

  • Adler, Thomas B.; Knizia, Gerald; Werner, Hans-Joachim
  • The Journal of Chemical Physics, Vol. 127, Issue 22
  • DOI: 10.1063/1.2817618

A complete basis set model chemistry. V. Extensions to six or more heavy atoms
journal, February 1996

  • Ochterski, Joseph W.; Petersson, G. A.; Montgomery, J. A.
  • The Journal of Chemical Physics, Vol. 104, Issue 7
  • DOI: 10.1063/1.470985

Theoretical studies of unimolecular reactions of C2–C5 alkoxy radicals. Part I. Ab initio molecular orbital calculations
journal, January 2000

  • Somnitz, H.; Zellner, R.
  • Physical Chemistry Chemical Physics, Vol. 2, Issue 9
  • DOI: 10.1039/b000037j

The β C–C bond scission in alkoxy radicals: thermal unimolecular decomposition of t-butoxy radicals
journal, January 2000

  • Fittschen, Christa; Hippler, Horst; Viskolcz, Be´la
  • Physical Chemistry Chemical Physics, Vol. 2, Issue 8
  • DOI: 10.1039/b000009o

A structure–activity relationship for the rate coefficient of H-migration in substituted alkoxy radicals
journal, January 2010

  • Vereecken, L.; Peeters, J.
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 39
  • DOI: 10.1039/c0cp00387e

Effectiveness of Diffuse Basis Functions for Calculating Relative Energies by Density Functional Theory
journal, March 2003

  • Lynch, Benjamin J.; Zhao, Yan; Truhlar, Donald G.
  • The Journal of Physical Chemistry A, Vol. 107, Issue 9
  • DOI: 10.1021/jp021590l

An Efficient and Accurate Formalism for the Treatment of Large Amplitude Intramolecular Motion
journal, July 2012

  • Reinisch, Guillaume; Miki, Kenji; Vignoles, Gérard L.
  • Journal of Chemical Theory and Computation, Vol. 8, Issue 8
  • DOI: 10.1021/ct300278x

Exploring the Limit of Accuracy of the Global Hybrid Meta Density Functional for Main-Group Thermochemistry, Kinetics, and Noncovalent Interactions
journal, October 2008

  • Zhao, Yan; Truhlar, Donald G.
  • Journal of Chemical Theory and Computation, Vol. 4, Issue 11
  • DOI: 10.1021/ct800246v

Local explicitly correlated second-order perturbation theory for the accurate treatment of large molecules
journal, February 2009

  • Adler, Thomas B.; Werner, Hans-Joachim; Manby, Frederick R.
  • The Journal of Chemical Physics, Vol. 130, Issue 5
  • DOI: 10.1063/1.3040174

A temperature-dependent relative-rate study of the OH initiated oxidation of n-butane: The kinetics of the reactions of the 1- and 2-butoxy radicals
journal, January 2005

  • Cassanelli, Paola; Johnson, D.; Anthony Cox, R.
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 21
  • DOI: 10.1039/b507137b

Group Additive Values for the Gas-Phase Standard Enthalpy of Formation, Entropy and Heat Capacity of Oxygenates
journal, October 2013

  • Paraskevas, Paschalis D.; Sabbe, Maarten K.; Reyniers, Marie-Françoise
  • Chemistry - A European Journal, Vol. 19, Issue 48
  • DOI: 10.1002/chem.201301381

The Penetration of a Potential Barrier by Electrons
journal, June 1930


A detailed experimental and theoretical study on the decomposition of methoxy radicals
journal, January 2001

  • Hippler, Horst; Striebel, Frank; Viskolcz, Be´la
  • Physical Chemistry Chemical Physics, Vol. 3, Issue 12
  • DOI: 10.1039/b101376i

MSTor: A program for calculating partition functions, free energies, enthalpies, entropies, and heat capacities of complex molecules including torsional anharmonicity
journal, August 2012

  • Zheng, Jingjing; Mielke, Steven L.; Clarkson, Kenneth L.
  • Computer Physics Communications, Vol. 183, Issue 8
  • DOI: 10.1016/j.cpc.2012.03.007

Kinetics of elementary reactions in low-temperature autoignition chemistry
journal, August 2011

  • Zádor, Judit; Taatjes, Craig A.; Fernandes, Ravi X.
  • Progress in Energy and Combustion Science, Vol. 37, Issue 4
  • DOI: 10.1016/j.pecs.2010.06.006

Ab Initio Kinetics for the Decomposition of Hydroxybutyl and Butoxy Radicals of n -Butanol
journal, February 2013

  • Zhang, Peng; Klippenstein, Stephen J.; Law, Chung K.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 9
  • DOI: 10.1021/jp400155z

Understanding low-temperature first-stage ignition delay: Propane
journal, October 2015


Ab initio statistical thermodynamical models for the computation of third-law entropies
journal, April 1997

  • East, Allan L. L.; Radom, Leo
  • The Journal of Chemical Physics, Vol. 106, Issue 16
  • DOI: 10.1063/1.473958

A shock tube and chemical kinetic modeling study of the pyrolysis and oxidation of butanols
journal, June 2012


Reactivity Trends within Alkoxy Radical Reactions Responsible for Chain Branching
journal, November 2011

  • Davis, Alexander C.; Francisco, Joseph S.
  • Journal of the American Chemical Society, Vol. 133, Issue 45
  • DOI: 10.1021/ja204806b

A complete basis set model chemistry. VI. Use of density functional geometries and frequencies
journal, February 1999

  • Montgomery, J. A.; Frisch, M. J.; Ochterski, J. W.
  • The Journal of Chemical Physics, Vol. 110, Issue 6
  • DOI: 10.1063/1.477924

Isomerization reactions of then-C4H9O andn-OOC4H8OH radicals in oxygen
journal, January 1996


Tunneling in Hydrogen-Transfer Isomerization of n -Alkyl Radicals
journal, December 2011

  • Sirjean, Baptiste; Dames, Enoch; Wang, Hai
  • The Journal of Physical Chemistry A, Vol. 116, Issue 1
  • DOI: 10.1021/jp209360u

Theoretical Study of the Thermodynamics and Kinetics of Hydrogen Abstractions from Hydrocarbons
journal, November 2007

  • Vandeputte, Aäron G.; Sabbe, Maarten K.; Reyniers, Marie-Françoise
  • The Journal of Physical Chemistry A, Vol. 111, Issue 46
  • DOI: 10.1021/jp075132u

A comprehensive chemical kinetic combustion model for the four butanol isomers
journal, June 2012


The thermal unimolecular decomposition rate constants of ethoxy radicals
journal, January 1999

  • Caralp, oise; Devolder, Pascal; Fittschen, Christa
  • Physical Chemistry Chemical Physics, Vol. 1, Issue 12
  • DOI: 10.1039/a901768b