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Title: The fate of the tert-butyl radical in low-temperature autoignition reactions

Abstract

Alkyl combustion models depend on kinetic parameters derived from reliable experimental or theoretical energetics that are often unavailable for larger species. Here, we have performed a comprehensive investigation of the tert-butyl radical ( R in this paper) autoignition pathways. CCSD(T)/ANO0 geometries and harmonic vibrational frequencies were obtained for key stationary points for the R + O2 and QOOH + O2 mechanisms. Relative energies were computed to chemical accuracy (±1 kcal mol-1) via extrapolation of RCCSD(T) energies to the complete basis-set limit, or usage of RCCSD(T)-F12 methods. At 0 K, the minimum energy R + O2 pathway involves direct elimination of HO$$^{•}_{2}$$ (30.3 kcal mol-1 barrier) from the tert-butyl peroxy radical ( ROO) to give isobutene. This pathway lies well below the competing QOOH-forming intramolecular hydrogen abstraction pathway (36.2 kcal mol-1 barrier) and ROO dissociation (35.9 kcal mol-1 barrier). The most favorable decomposition channel for QOOH radicals leads to isobutene oxide (12.0 kcal mol-1 barrier) over isobutene (18.6 kcal mol-1 barrier). For the QOOH + O2 pathways, we studied the transition states and initial products along three pathways: (1) α-hydrogen abstraction (42.0 kcal mol-1 barrier), (2) γ-hydrogen abstraction (27.0 kcal mol-1 barrier), and (3) hydrogen transfer to the peroxy moiety (24.4 kcal mol-1 barrier). The barrier is an extensive modification to the previous 18.7 kcal mol-1 value and warrants further study. However, it is still likely that the lowest energy QOOH + O2 pathway corresponds to pathway (3). We found significant spin contamination and/or multireference character in multiple stationary points, especially for transition states stemming from QOOH. Lastly, we provide evidence for an $$\tilde{A} - \tilde{X}$$ surface crossing at a Cs-symmetric, intramolecular hydrogen abstraction structure.

Authors:
 [1]; ORCiD logo [1];  [1]
  1. Univ. of Georgia, Athens, GA (United States). Center for Computational Quantum Chemistry
Publication Date:
Research Org.:
Univ. of Georgia, Athens, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1535310
Alternate Identifier(s):
OSTI ID: 1361876
Grant/Contract Number:  
FG02-97ER14748; FG02-97-ER14748
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 19; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
chemistry; physics

Citation Formats

Moore, Kevin B., Turney, Justin M., and Schaefer, Henry F. The fate of the tert-butyl radical in low-temperature autoignition reactions. United States: N. p., 2017. Web. doi:10.1063/1.4983128.
Moore, Kevin B., Turney, Justin M., & Schaefer, Henry F. The fate of the tert-butyl radical in low-temperature autoignition reactions. United States. doi:10.1063/1.4983128.
Moore, Kevin B., Turney, Justin M., and Schaefer, Henry F. Wed . "The fate of the tert-butyl radical in low-temperature autoignition reactions". United States. doi:10.1063/1.4983128. https://www.osti.gov/servlets/purl/1535310.
@article{osti_1535310,
title = {The fate of the tert-butyl radical in low-temperature autoignition reactions},
author = {Moore, Kevin B. and Turney, Justin M. and Schaefer, Henry F.},
abstractNote = {Alkyl combustion models depend on kinetic parameters derived from reliable experimental or theoretical energetics that are often unavailable for larger species. Here, we have performed a comprehensive investigation of the tert-butyl radical (R• in this paper) autoignition pathways. CCSD(T)/ANO0 geometries and harmonic vibrational frequencies were obtained for key stationary points for the R• + O2 and QOOH + O2 mechanisms. Relative energies were computed to chemical accuracy (±1 kcal mol-1) via extrapolation of RCCSD(T) energies to the complete basis-set limit, or usage of RCCSD(T)-F12 methods. At 0 K, the minimum energy R• + O2 pathway involves direct elimination of HO$^{•}_{2}$ (30.3 kcal mol-1 barrier) from the tert-butyl peroxy radical (ROO•) to give isobutene. This pathway lies well below the competing QOOH-forming intramolecular hydrogen abstraction pathway (36.2 kcal mol-1 barrier) and ROO• dissociation (35.9 kcal mol-1 barrier). The most favorable decomposition channel for QOOH radicals leads to isobutene oxide (12.0 kcal mol-1 barrier) over isobutene (18.6 kcal mol-1 barrier). For the QOOH + O2 pathways, we studied the transition states and initial products along three pathways: (1) α-hydrogen abstraction (42.0 kcal mol-1 barrier), (2) γ-hydrogen abstraction (27.0 kcal mol-1 barrier), and (3) hydrogen transfer to the peroxy moiety (24.4 kcal mol-1 barrier). The barrier is an extensive modification to the previous 18.7 kcal mol-1 value and warrants further study. However, it is still likely that the lowest energy QOOH + O2 pathway corresponds to pathway (3). We found significant spin contamination and/or multireference character in multiple stationary points, especially for transition states stemming from QOOH. Lastly, we provide evidence for an $\tilde{A} - \tilde{X}$ surface crossing at a Cs-symmetric, intramolecular hydrogen abstraction structure.},
doi = {10.1063/1.4983128},
journal = {Journal of Chemical Physics},
number = 19,
volume = 146,
place = {United States},
year = {2017},
month = {5}
}

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Works referenced in this record:

Thermochemistry of the R−O 2 Bond in Alkyl and Chloroalkyl Peroxy Radicals
journal, March 1998

  • Knyazev, Vadim D.; Slagle, Irene R.
  • The Journal of Physical Chemistry A, Vol. 102, Issue 10
  • DOI: 10.1021/jp9726091

Near-IR Cavity Ringdown Spectroscopy and Kinetics of the Isomers and Conformers of the Butyl Peroxy Radical
journal, December 2005

  • Glover, Brent G.; Miller, Terry A.
  • The Journal of Physical Chemistry A, Vol. 109, Issue 49
  • DOI: 10.1021/jp054838q

Kinetics and branching ratio studies of the reaction of C2H5O2 + HO2 using chemical ionisation mass spectrometry
journal, January 2007

  • Teresa Raventós-Duran, M.; Percival, Carl J.; McGillen, Max R.
  • Physical Chemistry Chemical Physics, Vol. 9, Issue 31
  • DOI: 10.1039/b703038j

Negative-Ion Photoelectron Spectroscopy, Gas-Phase Acidity, and Thermochemistry of the Peroxyl Radicals CH 3 OO and CH 3 CH 2 OO
journal, October 2001

  • Blanksby, Stephen J.; Ramond, Tanya M.; Davico, Gustavo E.
  • Journal of the American Chemical Society, Vol. 123, Issue 39
  • DOI: 10.1021/ja010942j

Infrared absorption spectrum of t-butylperoxy radicals in the gas phase
journal, November 1975


The C 2 H 5 + O 2 Reaction Mechanism:  High-Level ab Initio Characterizations
journal, November 2000

  • Rienstra-Kiracofe, Jonathan C.; Allen, Wesley D.; Schaefer, Henry F.
  • The Journal of Physical Chemistry A, Vol. 104, Issue 44
  • DOI: 10.1021/jp001041k

Coupled cluster theory for high spin, open shell reference wave functions
journal, October 1993

  • Knowles, Peter J.; Hampel, Claudia; Werner, Hans‐Joachim
  • The Journal of Chemical Physics, Vol. 99, Issue 7
  • DOI: 10.1063/1.465990

Enthalpies of Formation and Bond Dissociation Energies of Lower Alkyl Hydroperoxides and Related Hydroperoxy and Alkoxy Radicals
journal, June 2008

  • Simmie, John M.; Black, Gráinne; Curran, Henry J.
  • The Journal of Physical Chemistry A, Vol. 112, Issue 22
  • DOI: 10.1021/jp711360z

An improvement of the resolution of the identity approximation for the formation of the Coulomb matrix
journal, September 2003

  • Neese, Frank
  • Journal of Computational Chemistry, Vol. 24, Issue 14
  • DOI: 10.1002/jcc.10318

Diode laser spectroscopy of the ν 3 and ν 2 fundamental bands of DO 2
journal, December 1985

  • Uehara, Hiromichi; Kawaguchi, Kentarou; Hirota, Eizi
  • The Journal of Chemical Physics, Vol. 83, Issue 11
  • DOI: 10.1063/1.449668

High-Pressure Rate Rules for Alkyl + O 2 Reactions. 1. The Dissociation, Concerted Elimination, and Isomerization Channels of the Alkyl Peroxy Radical
journal, November 2011

  • Villano, Stephanie M.; Huynh, Lam K.; Carstensen, Hans-Heinrich
  • The Journal of Physical Chemistry A, Vol. 115, Issue 46
  • DOI: 10.1021/jp2079204

Infra-red cryogenic studies. Part 12.—Alkenes in argon matrices
journal, January 1973

  • Barnes, A. J.; Howells, J. D. R.
  • J. Chem. Soc., Faraday Trans. 2, Vol. 69, Issue 0
  • DOI: 10.1039/f29736900532

Thermochemistry, Reaction Paths, and Kinetics on the tert -Isooctane Radical Reaction with O 2
journal, June 2014

  • Snitsiriwat, Suarwee; Bozzelli, Joseph W.
  • The Journal of Physical Chemistry A, Vol. 118, Issue 26
  • DOI: 10.1021/jp502702f

Addition of i-butane to slowly reacting mixtures of hydrogen and oxygen at 480°C
journal, January 1978

  • Baker, Richard R.; Baldwin, Roy R.; Walker, Raymond W.
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 74, Issue 0
  • DOI: 10.1039/f19787402229

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

Isobutane ignition delay time measurements at high pressure and detailed chemical kinetic simulations
journal, August 2010


781. Slow oxidation of hydrocarbons in the gas phase. Part I. Reactions during the induction period of isobutane oxidation
journal, January 1961

  • Zeelenberg, A. P.; Bickel, A. F.
  • Journal of the Chemical Society (Resumed)
  • DOI: 10.1039/jr9610004014

Self‐consistent molecular orbital methods. XVIII. Constraints and stability in Hartree–Fock theory
journal, April 1977

  • Seeger, Rolf; Pople, John A.
  • The Journal of Chemical Physics, Vol. 66, Issue 7
  • DOI: 10.1063/1.434318

A second order multiconfiguration SCF procedure with optimum convergence
journal, June 1985

  • Werner, Hans‐Joachim; Knowles, Peter J.
  • The Journal of Chemical Physics, Vol. 82, Issue 11
  • DOI: 10.1063/1.448627

The decomposition of 2,2,3,3-tetramethylbutane in KCl- and B2O3-coated vessels in the presence of oxygen
journal, January 1982

  • Baldwin, Roy R.; Hisham, Mohamed W. M.; Keen, Alan
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 78, Issue 4
  • DOI: 10.1039/f19827801165

Photoelectron spectroscopy, gas phase acidity, and thermochemistry of tert -butyl hydroperoxide: Mechanisms for the rearrangement of peroxyl radicals
journal, December 1998

  • Clifford, Eileen P.; Wenthold, Paul G.; Gareyev, Roustam
  • The Journal of Chemical Physics, Vol. 109, Issue 23
  • DOI: 10.1063/1.477725

Peroxy radicals
journal, January 1969


Hartree–Fock orbital instability envelopes in highly correlated single-reference wave functions
journal, December 1997

  • Crawford, T. Daniel; Stanton, John F.; Allen, Wesley D.
  • The Journal of Chemical Physics, Vol. 107, Issue 24
  • DOI: 10.1063/1.474178

The diagonal correction to the Born–Oppenheimer approximation: Its effect on the singlet–triplet splitting of CH 2 and other molecular effects
journal, April 1986

  • Handy, Nicholas C.; Yamaguchi, Yukio; Schaefer, Henry F.
  • The Journal of Chemical Physics, Vol. 84, Issue 8
  • DOI: 10.1063/1.450020

An overlap fitted chain of spheres exchange method
journal, October 2011

  • Izsák, Róbert; Neese, Frank
  • The Journal of Chemical Physics, Vol. 135, Issue 14
  • DOI: 10.1063/1.3646921

Product formation in the slow oxidation of isobutane
journal, January 1981


Effect of the damping function in dispersion corrected density functional theory
journal, March 2011

  • Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars
  • Journal of Computational Chemistry, Vol. 32, Issue 7
  • DOI: 10.1002/jcc.21759

Definitive Ab Initio Studies of Model SN2 Reactions CH3X+F (X=F, Cl, CN, OH, SH, NH2, PH2)
journal, May 2003

  • Gonzales, Jason M.; Pak, Chaeho; Cox, R. Sidney
  • Chemistry - A European Journal, Vol. 9, Issue 10
  • DOI: 10.1002/chem.200204408

Alkylperoxy and alkyl radicals. 5. IR spectra and UV photolysis of tert-butylperoxy radicals in argon plus oxygen matrixes
journal, November 1987

  • Chettur, G.; Snelson, A.
  • The Journal of Physical Chemistry, Vol. 91, Issue 23
  • DOI: 10.1021/j100307a012

Formation of hydrocarbons and oxides of nitrogen in automobile engines
journal, March 1973

  • Heywood, John B.; Keck, James C.
  • Environmental Science & Technology, Vol. 7, Issue 3
  • DOI: 10.1021/es60075a002

Comparison of two efficient approximate Hartee–Fock approaches
journal, October 2009


Erratum: “Coupled cluster theory for high spin, open shell reference wave functions” [ J. Chem. Phys. 99 , 5219 (1993)]
journal, February 2000

  • Knowles, Peter J.; Hampel, Claudia; Werner, Hans-Joachim
  • The Journal of Chemical Physics, Vol. 112, Issue 6
  • DOI: 10.1063/1.480886

Additional chain-branching pathways in the low-temperature oxidation of branched alkanes
journal, February 2016


Ignition properties of n-butane and iso-butane in a rapid compression machine
journal, February 2010


The heat of formation of NCO
journal, September 1993

  • East, Allan L. L.; Allen, Wesley D.
  • The Journal of Chemical Physics, Vol. 99, Issue 6
  • DOI: 10.1063/1.466062

Structure of Isobutylene
journal, October 1963

  • Scharpen, LeRoy H.; Laurie, Victor W.
  • The Journal of Chemical Physics, Vol. 39, Issue 7
  • DOI: 10.1063/1.1734521

280. Detection of the epoxide group by infrared spectroscopy
journal, January 1957

  • Henbest, H. B.; Meakins, G. D.; Nicholls, B.
  • Journal of the Chemical Society (Resumed)
  • DOI: 10.1039/jr9570001459

270. Radical isomerisation during the gaseous oxidation of 2,3-dimethylbutane
journal, January 1963


General contraction of Gaussian basis sets. I. Atomic natural orbitals for first‐ and second‐row atoms
journal, April 1987

  • Almlöf, Jan; Taylor, Peter R.
  • The Journal of Chemical Physics, Vol. 86, Issue 7
  • DOI: 10.1063/1.451917

Direct observation and kinetics of a hydroperoxyalkyl radical (QOOH)
journal, February 2015


Fundamental phenomena affecting low temperature combustion and HCCI engines, high load limits and strategies for extending these limits
journal, October 2013


Establishment of the C2H5+O2 reaction mechanism: A combustion archetype
journal, February 2008

  • Wilke, Jeremiah J.; Allen, Wesley D.; Schaefer, Henry F.
  • The Journal of Chemical Physics, Vol. 128, Issue 7
  • DOI: 10.1063/1.2827133

Non-iterative fifth-order triple and quadruple excitation energy corrections in correlated methods
journal, February 1990


A fifth-order perturbation comparison of electron correlation theories
journal, May 1989


Infrared matrix isolation studies on the t ‐butyl radical
journal, May 1981

  • Pacansky, J.; Chang, J. S.
  • The Journal of Chemical Physics, Vol. 74, Issue 10
  • DOI: 10.1063/1.440916

Analytical energy gradients for multiconfiguration self‐consistent field wave functions with frozen core orbitals
journal, May 1991

  • Busch, Thilo; Esposti, Alessandra Degli; Werner, Hans‐Joachim
  • The Journal of Chemical Physics, Vol. 94, Issue 10
  • DOI: 10.1063/1.460247

Reactions of isobutane and the tert-butyl radical with atomic and molecular oxygen
journal, May 1980

  • Washida, Nobuaki; Bayes, Kyle D.
  • The Journal of Physical Chemistry, Vol. 84, Issue 11
  • DOI: 10.1021/j100448a004

Can coupled-cluster theory treat conical intersections?
journal, July 2007

  • Köhn, Andreas; Tajti, Attila
  • The Journal of Chemical Physics, Vol. 127, Issue 4
  • DOI: 10.1063/1.2755681

Role of O 2 + QOOH in Low-Temperature Ignition of Propane. 1. Temperature and Pressure Dependent Rate Coefficients
journal, March 2012

  • Goldsmith, C. Franklin; Green, William H.; Klippenstein, Stephen J.
  • The Journal of Physical Chemistry A, Vol. 116, Issue 13
  • DOI: 10.1021/jp210722w

Analysis of Tertiary Butyl Radical + O 2 , Isobutene + HO 2 , Isobutene + OH, and Isobutene−OH Adducts + O 2 :  A Detailed Tertiary Butyl Oxidation Mechanism
journal, December 1999

  • Chen, Chiung-Ju; Bozzelli, Joseph W.
  • The Journal of Physical Chemistry A, Vol. 103, Issue 48
  • DOI: 10.1021/jp991227n

Rates of reaction of butyl radicals with molecular oxygen
journal, January 1980

  • Lenhardt, Terence M.; McDade, Charles E.; Bayes, Kyle D.
  • The Journal of Chemical Physics, Vol. 72, Issue 1
  • DOI: 10.1063/1.438848

Detailed kinetic mechanism of the multistage oxidation and combustion of isobutane
journal, March 2015

  • Basevich, V. Ya.; Belyaev, A. A.; Medvedev, S. N.
  • Russian Journal of Physical Chemistry B, Vol. 9, Issue 2
  • DOI: 10.1134/s1990793115020177

First-Principles Dynamics along the Reaction Path of CH 3 CH 2 + O 2 → H 2 C=CH 2 + HOO:  Evidence for Vibronic State Mixing and Neutral Hydrogen Transfer
journal, October 2002

  • Andersen, Amity; Carter, Emily A.
  • The Journal of Physical Chemistry A, Vol. 106, Issue 42
  • DOI: 10.1021/jp0206267

The ORCA program system: The ORCA program system
journal, June 2011

  • Neese, Frank
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 1
  • DOI: 10.1002/wcms.81

FTIR product study of the reaction of C2H5O2+HO2 in air at 295 K
journal, March 1990


Chemical Kinetic Data Base for Combustion Chemistry Part 4. Isobutane
journal, January 1990

  • Tsang, Wing
  • Journal of Physical and Chemical Reference Data, Vol. 19, Issue 1
  • DOI: 10.1063/1.555877

Reaction of t-butyl radicals with hydrogen and with oxygen
journal, January 1979

  • Evans, Geoffrey A.; Walker, Raymond W.
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 75, Issue 0
  • DOI: 10.1039/f19797501458

Addition of Peroxyl Radicals to Alkenes and the Reaction of Oxygen with Alkyl Radicals
journal, May 2000

  • Stark, Moray S.
  • Journal of the American Chemical Society, Vol. 122, Issue 17
  • DOI: 10.1021/ja993760m

Reaction of CH3O2+HO2 in air at 295 K: A product study
journal, April 1990


In pursuit of the ab initio limit for conformational energy prototypes
journal, June 1998

  • Császár, Attila G.; Allen, Wesley D.; Schaefer, Henry F.
  • The Journal of Chemical Physics, Vol. 108, Issue 23
  • DOI: 10.1063/1.476449

Third O2 addition reactions promote the low-temperature auto-ignition of n-alkanes
journal, March 2016


Examining the ground and first excited states of methyl peroxy radical with high-level coupled-cluster theory
journal, July 2015


The oxidation of isobutane
journal, January 1959


Directly measuring reaction kinetics of ˙QOOH – a crucial but elusive intermediate in hydrocarbon autoignition
journal, January 2013

  • Zádor, Judit; Huang, Haifeng; Welz, Oliver
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 26
  • DOI: 10.1039/c3cp51185e

Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989

  • Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 90, Issue 2
  • DOI: 10.1063/1.456153

Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988


Anatomy of relativistic energy corrections in light molecular systems
journal, November 2001


Psi4: an open-source ab initio electronic structure program : Psi4: an electronic structure program
journal, October 2011

  • Turney, Justin M.; Simmonett, Andrew C.; Parrish, Robert M.
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 4
  • DOI: 10.1002/wcms.93

A Theoretical Investigation of the Gas-Phase Oxidation Reaction of the Saturated tert-Butyl Radical
journal, November 2006


Analysis of the structures, infrared spectra, and Raman spectra for methyl, ethyl, isopropyl, and tert-butyl radicals
journal, January 1991

  • Pacansky, Jacob; Koch, W.; Miller, M. D.
  • Journal of the American Chemical Society, Vol. 113, Issue 1
  • DOI: 10.1021/ja00001a046

Addition of 2,2,3,3-tetramethylbutane to slowly reacting mixtures of hydrogen and oxygen
journal, January 1979

  • Baldwin, Roy R.; Walker, Raymond W.; Walker, Robert W.
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 75, Issue 0
  • DOI: 10.1039/f19797501447

Fuel reactivity controlled compression ignition (RCCI): a pathway to controlled high-efficiency clean combustion
journal, June 2011

  • Kokjohn, S. L.; Hanson, R. M.; Splitter, D. A.
  • International Journal of Engine Research, Vol. 12, Issue 3
  • DOI: 10.1177/1468087411401548

Decomposition of 2,2,3,3-tetramethylbutane in the presence of oxygen
journal, January 1978

  • Atri, Gulshan M.; Baldwin, Roy R.; Evans, Geoffrey A.
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 74, Issue 0
  • DOI: 10.1039/f19787400366

Sources of error in electronic structure calculations on small chemical systems
journal, February 2006

  • Feller, David; Peterson, Kirk A.; Crawford, T. Daniel
  • The Journal of Chemical Physics, Vol. 124, Issue 5
  • DOI: 10.1063/1.2137323

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005

  • Weigend, Florian; Ahlrichs, Reinhart
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
  • DOI: 10.1039/b508541a

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

Stability conditions for the solutions of the Hartree-Fock equations for the simple open-shell case
journal, January 1969


Kinetic studies of reactions of the nitrate radical (NO3) with peroxy radicals (RO2): an indirect source of OH at night?
journal, January 2006

  • Vaughan, Stewart; Canosa-Mas, Carlos E.; Pfrang, Christian
  • Physical Chemistry Chemical Physics, Vol. 8, Issue 32
  • DOI: 10.1039/b605569a

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

Microwave Spectrum of Isobutylene. Dipole Moment, Internal Barrier, Equilibrium Conformation, and Structure
journal, May 1961

  • Laurie, Victor W.
  • The Journal of Chemical Physics, Vol. 34, Issue 5
  • DOI: 10.1063/1.1701038

The structure of 2,2-dimethyloxirane obtained by microwave spectroscopy
journal, April 1997


Open‐shell coupled‐cluster theory
journal, June 1993

  • Jayatilaka, Dylan; Lee, Timothy J.
  • The Journal of Chemical Physics, Vol. 98, Issue 12
  • DOI: 10.1063/1.464352

General atomic and molecular electronic structure system
journal, November 1993

  • Schmidt, Michael W.; Baldridge, Kim K.; Boatz, Jerry A.
  • Journal of Computational Chemistry, Vol. 14, Issue 11, p. 1347-1363
  • DOI: 10.1002/jcc.540141112

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
  • DOI: 10.1063/1.470645

Free radical autoxidations of hydrocarbons
journal, July 1968


Hindered Rotation of the Methyl Groups in Ethane
journal, November 1936

  • Kemp, J. D.; Pitzer, Kenneth S.
  • The Journal of Chemical Physics, Vol. 4, Issue 11
  • DOI: 10.1063/1.1749784

Synchrotron photoionization measurements of fundamental autoignition reactions: Product formation in low-temperature isobutane oxidation
journal, January 2013

  • Eskola, Arkke J.; Welz, Oliver; Savee, John D.
  • Proceedings of the Combustion Institute, Vol. 34, Issue 1
  • DOI: 10.1016/j.proci.2012.06.116

Review of high efficiency and clean reactivity controlled compression ignition (RCCI) combustion in internal combustion engines
journal, February 2015


The ν 1 band of the DO 2 radical by difference frequency laser and diode laser spectroscopy: The equilibrium structure of the hydroperoxyl radical
journal, December 1984

  • Lubic, Karen G.; Amano, Takayoshi; Uehara, Hiromichi
  • The Journal of Chemical Physics, Vol. 81, Issue 11
  • DOI: 10.1063/1.447508

A diagnostic for determining the quality of single-reference electron correlation methods
journal, April 1989

  • Lee, Timothy J.; Taylor, Peter R.
  • International Journal of Quantum Chemistry, Vol. 36, Issue S23
  • DOI: 10.1002/qua.560360824

Predicting chemical kinetics with computational chemistry: is QOOH→HOQO important in fuel ignition?
journal, February 2004


Infrared spectra of the isobutyl and neopentyl radicals. Characteristic spectra of primary, secondary, and tertiary alkyl radicals
journal, August 1981

  • Pacansky, J.; Brown, D. W.; Chang, J. S.
  • The Journal of Physical Chemistry, Vol. 85, Issue 17
  • DOI: 10.1021/j150617a029

Infrared Absorption Bands Characteristic of Oxirane Ring
journal, May 1954


Basis-set convergence of correlated calculations on water
journal, June 1997

  • Helgaker, Trygve; Klopper, Wim; Koch, Henrik
  • The Journal of Chemical Physics, Vol. 106, Issue 23
  • DOI: 10.1063/1.473863

Kinetics of the CH3O2 + HO2 reaction: A temperature and pressure dependence study using chemical ionization mass spectrometry
journal, January 2007

  • Raventós-Duran, M. Teresa; McGillen, Max; Percival, Carl J.
  • International Journal of Chemical Kinetics, Vol. 39, Issue 10
  • DOI: 10.1002/kin.20269

Parallel Calculation of CCSD and CCSD(T) Analytic First and Second Derivatives
journal, November 2007

  • Harding, Michael E.; Metzroth, Thorsten; Gauss, Jürgen
  • Journal of Chemical Theory and Computation, Vol. 4, Issue 1
  • DOI: 10.1021/ct700152c

An efficient linear-scaling CCSD(T) method based on local natural orbitals
journal, September 2013

  • Rolik, Zoltán; Szegedy, Lóránt; Ladjánszki, István
  • The Journal of Chemical Physics, Vol. 139, Issue 9
  • DOI: 10.1063/1.4819401

Toward subchemical accuracy in computational thermochemistry: Focal point analysis of the heat of formation of NCO and [H,N,C,O] isomers
journal, June 2004

  • Schuurman, Michael S.; Muir, Steven R.; Allen, Wesley D.
  • The Journal of Chemical Physics, Vol. 120, Issue 24
  • DOI: 10.1063/1.1707013