The multichannel $n$-propyl + O2 reaction surface: Definitive theory on a model hydrocarbon oxidation mechanism

Bartlett, Marcus A.; Liang, Tao; Pu, Liang; Schaefer, Henry F.; Allen, Wesley D.

doi:10.1063/1.5017305

Title: The multichannel $$n$$-propyl + O₂ reaction surface: Definitive theory on a model hydrocarbon oxidation mechanism

Abstract

The n-propyl + O₂ reaction is an important model of chain branching reactions in larger combustion systems. In this work, focal point analyses (FPAs) extrapolating to the ab initio limit were performed on the n-propyl + O₂ system based on explicit quantum chemical computations with electron correlation treatments through coupled cluster single, double, triple, and perturbative quadruple excitations [CCSDT(Q)] and basis sets up to cc-pV5Z. All reaction species and transition states were fully optimized at the rigorous CCSD(T)/cc-pVTZ level of theory, revealing some substantial differences in comparison to the density functional theory geometries existing in the literature. A mixed Hessian methodology was implemented and benchmarked that essentially makes the computations of CCSD(T)/cc-pVTZ vibrational frequencies feasible and thus provides critical improvements to zero-point vibrational energies for the n-propyl + O₂ system. Two key stationary points, n-propylperoxy radical (MIN1) and its concerted elimination transition state (TS1), were located 32.7 kcal mol^-1 and 2.4 kcal mol^-1 below the reactants, respectively. Two competitive $$β$$-hydrogen transfer transition states (TS2 and TS2') were found separated by only 0.16 kcal mol^-1, a fact unrecognized in the current combustion literature. Incorporating TS2' in master equation (ME) kinetic models might reduce the large discrepancy of 2.5 kcal mol^-1 betweenmore »« less

Authors:

Bartlett, Marcus A. ^[1]; Liang, Tao ^[1]; Pu, Liang ^[2]; Schaefer, Henry F. ^[1]; Allen, Wesley D. ^[1]

Univ. of Georgia, Athens, GA (United States). Dept. of Chemistry, Center for Computational Chemistry
Northwest A&F Univ., Shaanxi (China). College of Chemistry & Pharmacy

Publication Date:: Fri Mar 02 00:00:00 EST 2018

Research Org.:: Univ. of Georgia, Athens, GA (United States); Univ. of California, Oakland, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC)

OSTI Identifier:: 1540155

Alternate Identifier(s):: OSTI ID: 1423507

Grant/Contract Number:: SC0018412; AC02-05CH11231; SC0015512

Resource Type:: Journal Article: Accepted Manuscript

Journal Name:: Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 148; Journal Issue: 9; Journal ID: ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Physics

Citation Formats


                    Bartlett, Marcus A., Liang, Tao, Pu, Liang, Schaefer, Henry F., and Allen, Wesley D. The multichannel $n$-propyl + O2 reaction surface: Definitive theory on a model hydrocarbon oxidation mechanism.  United States: N. p., 2018. 
        Web.  doi:10.1063/1.5017305.

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                    Bartlett, Marcus A., Liang, Tao, Pu, Liang, Schaefer, Henry F., & Allen, Wesley D. The multichannel $n$-propyl + O2 reaction surface: Definitive theory on a model hydrocarbon oxidation mechanism.  United States.  https://doi.org/10.1063/1.5017305

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                    Bartlett, Marcus A., Liang, Tao, Pu, Liang, Schaefer, Henry F., and Allen, Wesley D. 2018.  
        "The multichannel $n$-propyl + O2 reaction surface: Definitive theory on a model hydrocarbon oxidation mechanism".  United States.  https://doi.org/10.1063/1.5017305.  https://www.osti.gov/servlets/purl/1540155.

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@article{osti_1540155,

  title        = {The multichannel $n$-propyl + O2 reaction surface: Definitive theory on a model hydrocarbon oxidation mechanism},

  author       = {Bartlett, Marcus A. and Liang, Tao and Pu, Liang and Schaefer, Henry F. and Allen, Wesley D.},

  abstractNote = {The n-propyl + O2 reaction is an important model of chain branching reactions in larger combustion systems. In this work, focal point analyses (FPAs) extrapolating to the ab initio limit were performed on the n-propyl + O2 system based on explicit quantum chemical computations with electron correlation treatments through coupled cluster single, double, triple, and perturbative quadruple excitations [CCSDT(Q)] and basis sets up to cc-pV5Z. All reaction species and transition states were fully optimized at the rigorous CCSD(T)/cc-pVTZ level of theory, revealing some substantial differences in comparison to the density functional theory geometries existing in the literature. A mixed Hessian methodology was implemented and benchmarked that essentially makes the computations of CCSD(T)/cc-pVTZ vibrational frequencies feasible and thus provides critical improvements to zero-point vibrational energies for the n-propyl + O2 system. Two key stationary points, n-propylperoxy radical (MIN1) and its concerted elimination transition state (TS1), were located 32.7 kcal mol-1 and 2.4 kcal mol-1 below the reactants, respectively. Two competitive $β$-hydrogen transfer transition states (TS2 and TS2') were found separated by only 0.16 kcal mol-1, a fact unrecognized in the current combustion literature. Incorporating TS2' in master equation (ME) kinetic models might reduce the large discrepancy of 2.5 kcal mol-1 between FPA and ME barrier heights for TS2. TS2 exhibits an anomalously large diagonal Born-Oppenheimer correction ($Δ$DBOC = 1.71 kcal mol-1), which is indicative of a nearby surface crossing and possible nonadiabatic reaction dynamics. The first systematic conformational search of three hydroperoxypropyl (QOOH) intermediates was completed, uncovering a total of 32 rotamers lying within 1.6 kcal mol-1 of their respective lowest-energy minima. Our definitive energetics for stationary points on the $n$-propyl + O2 potential energy surface provide key benchmarks for future studies of hydrocarbon oxidation.},

  doi          = {10.1063/1.5017305},

  url          = {https://www.osti.gov/biblio/1540155},
  journal      = {Journal of Chemical Physics},

  issn         = {0021-9606},

  number       = 9,

  volume       = 148,

  place        = {United States},

  year         = {Fri Mar 02 00:00:00 EST 2018},

  month        = {Fri Mar 02 00:00:00 EST 2018}

}

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Works referencing / citing this record:

High-level theoretical characterization of the vinoxy radical ( ^• CH ₂ CHO) + O ₂ reaction
journal, May 2018

Weidman, Jared D.; Allen, Ryan T.; Moore, Kevin B.
The Journal of Chemical Physics, Vol. 148, Issue 18
https://doi.org/10.1063/1.5026295

Riddles of the structure and vibrational dynamics of HO ₃ resolved near the ab initio limit
journal, September 2019

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https://doi.org/10.1063/1.5110291

Characterization of the 2-methylvinoxy radical + O ₂ reaction: A focal point analysis and composite multireference study
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The Journal of Chemical Physics, Vol. 151, Issue 12
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Title: The multichannel $$n$$-propyl + O2 reaction surface: Definitive theory on a model hydrocarbon oxidation mechanism

Abstract

Citation Formats

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Theoretical Determinations of the Ambient Conformational Distribution and Unimolecular Decomposition of n -Propylperoxy Radical journal, April 2005

Formation of C 3 H 6 from the Reaction C 3 H 7 + O 2 and C 2 H 3 Cl from C 2 H 4 Cl + O 2 at 297 K journal, January 1996

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An alternative calculation of the vibrational potential energy distribution journal, November 1971

Measurements and Modeling of HO 2 Formation in the Reactions of n- C 3 H 7 and i- C 3 H 7 Radicals with O 2 † journal, May 2005

Aspects of the Reaction Mechanism of Ethane Combustion. 2. Nature of the Intramolecular Hydrogen Transfer journal, June 1994

Mechanism of the C2H5+O2 reaction journal, July 1997

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

Detailed Modeling of Low-Temperature Propane Oxidation: 1. The Role of the Propyl + O 2 Reaction journal, June 2010

Self‐Consistent Orbitals for Radicals journal, March 1954

Formation of C 3 H 6 from the Reaction C 3 H 7 + O 2 between 450 and 550 K journal, July 1998

Centrifugal distortion constants and structural parameters of methyl oxirane journal, February 1977

Conformational analysis of the 1- and 2-propyl peroxy radicals journal, April 2005

Application of systematic sequences of wave functions to the water dimer journal, April 1992

Kinetics of polyatomic free radicals produced by laser photolysis. 4. Study of the equilibrium isopropyl + oxygen .tautm. isopropylperoxy between 592 and 692 K journal, April 1985

The heat of formation of NCO journal, September 1993

Synchrotron Photoionization Mass Spectrometry Measurements of Product Formation in Low-Temperature n -Butane Oxidation: Toward a Fundamental Understanding of Autoignition Chemistry and n -C 4 H 9 + O 2 / s -C 4 H 9 + O 2 Reactions journal, November 2013

Theory, measurements, and modeling of OH and HO2 formation in the reaction of cyclohexyl radicals with O2 journal, January 2007

Some features of the oxidation of propane and ethane at 318°C journal, January 1959

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

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Molecular Structure of Propylene journal, October 1961

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Title: The multichannel $$n$$-propyl + O₂ reaction surface: Definitive theory on a model hydrocarbon oxidation mechanism

Conformers of Gaseous Cysteine
journal, May 2009

Theoretical Determinations of the Ambient Conformational Distribution and Unimolecular Decomposition of n -Propylperoxy Radical
journal, April 2005

Formation of C ₃ H ₆ from the Reaction C ₃ H ₇ + O ₂ and C ₂ H ₃ Cl from C ₂ H ₄ Cl + O ₂ at 297 K
journal, January 1996

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journal, November 2016

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journal, April 2001

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journal, November 2000

From theoretical reaction dynamics to chemical modeling of combustion
journal, January 2017

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journal, February 1982

Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis
journal, August 1980

A flow reactor study of neopentane oxidation at 8 atmospheres: experiments and modeling
journal, August 1999

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journal, July 2005

Wave function continuity and the diagonal Born-Oppenheimer correction at conical intersections
journal, May 2016

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journal, November 2005

On the accuracy of molecular properties by coupled-cluster methods for some difficult examples: Oxygen atom, iron atom, and cyano radical
journal, September 1994

Comment on: “Estimating the Hartree–Fock limit from finite basis set calculations” [Jensen F (2005) Theor Chem Acc 113:267]
journal, December 2005

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

An alternative calculation of the vibrational potential energy distribution
journal, November 1971

Measurements and Modeling of HO ₂ Formation in the Reactions of n- C ₃ H ₇ and i- C ₃ H ₇ Radicals with O ₂ ^†
journal, May 2005

Aspects of the Reaction Mechanism of Ethane Combustion. 2. Nature of the Intramolecular Hydrogen Transfer
journal, June 1994

Mechanism of the C2H5+O2 reaction
journal, July 1997

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

Detailed Modeling of Low-Temperature Propane Oxidation: 1. The Role of the Propyl + O ₂ Reaction
journal, June 2010

Self‐Consistent Orbitals for Radicals
journal, March 1954

Formation of C ₃ H ₆ from the Reaction C ₃ H ₇ + O ₂ between 450 and 550 K
journal, July 1998

Centrifugal distortion constants and structural parameters of methyl oxirane
journal, February 1977

Conformational analysis of the 1- and 2-propyl peroxy radicals
journal, April 2005

Application of systematic sequences of wave functions to the water dimer
journal, April 1992

Kinetics of polyatomic free radicals produced by laser photolysis. 4. Study of the equilibrium isopropyl + oxygen .tautm. isopropylperoxy between 592 and 692 K
journal, April 1985

The heat of formation of NCO
journal, September 1993

Synchrotron Photoionization Mass Spectrometry Measurements of Product Formation in Low-Temperature n -Butane Oxidation: Toward a Fundamental Understanding of Autoignition Chemistry and n -C ₄ H ₉ + O ₂ / s -C ₄ H ₉ + O ₂ Reactions
journal, November 2013

Theory, measurements, and modeling of OH and HO2 formation in the reaction of cyclohexyl radicals with O2
journal, January 2007

Some features of the oxidation of propane and ethane at 318°C
journal, January 1959

Study of the Low Temperature Oxidation of Propane
journal, December 2012

Formally direct pathways and low-temperature chain branching in hydrocarbon autoignition: the cyclohexyl + O2 reaction at high pressure
journal, January 2009

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

Aspects of the reaction mechanism of ethane combustion. Conformations of the ethylperoxy radical
journal, October 1992

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

Uncovering the Fundamental Chemistry of Alkyl + O ₂ Reactions via Measurements of Product Formation
journal, April 2006

Many-body perturbation theory with a restricted open-shell Hartree—Fock reference
journal, November 1991

An open-shell restricted Hartree—Fock perturbation theory based on symmetric spin orbitals
journal, January 1993

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

Relative rate study of the addition of HO2 radicals to C2H4 and C3H6
journal, January 1986

Advances in electronic structure theory
book, January 2005

Molecular Spectra and Molecular Structure
book, January 1979

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

Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994

The reaction between ethyl and molecular oxygen II: Further analysis
journal, January 2001

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

Oxidation of n-Butane: Transition in the Mechanism across the Region of Negative Temperature Coefficient
journal, July 1995

Systematic Computational Study on the Unimolecular Reactions of Alkylperoxy (RO ₂ ), Hydroperoxyalkyl (QOOH), and Hydroperoxyalkylperoxy (O ₂ QOOH) Radicals
journal, April 2011

Infrared Frequency-Modulation Probing of Product Formation in Alkyl + O ₂ Reactions: III. The Reaction of Cyclopentyl Radical ( c -C ₅ H ₉ ) with O ₂ between 296 and 723 K
journal, July 2001

Time-resolved measurements of OH and HO2 product formation in pulsed-photolytic chlorine atom initiated oxidation of neopentane
journal, March 2003

The full CCSDT model for molecular electronic structure
journal, June 1987

Impact of tunneling on hydrogen-migration of the n-propylperoxy radical
journal, January 2011

Uncertainty propagation in the derivation of phenomenological rate coefficients from theory: A case study of n-propyl radical oxidation
journal, January 2013

Experimental investigation of the kinetics and mechanism of the reaction of n-propyl radicals with molecular oxygen from 297 to 635 K
journal, January 1985

A new mechanism for the low temperature oxidation of hydrocarbons in the gas phase
journal, September 1965

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journal, April 1960

The mechanism of oxidation of alkanes in the gas phase
journal, January 1965

Measurements and Modeling of DO ₂ Formation in the Reactions of C ₂ D ₅ and C ₃ D ₇ Radicals with O ₂ ^†
journal, May 2007

Benchmark calculations with correlated molecular wave functions. IV. The classical barrier height of the H+H ₂ →H ₂ +H reaction
journal, May 1994

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Cysteine conformations revisited
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Ab initio total atomization energies of small molecules — towards the basis set limit
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Molecular structure of oxetane
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Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
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A reduced reaction mechanism for the combustion of n-butane
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Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions
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Measurements and Automated Mechanism Generation Modeling of OH Production in Photolytically Initiated Oxidation of the Neopentyl Radical ^‖
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Arrhenius parameters for the reaction i-C3H7+ O2? C3H6+ HO2
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New Insights into Low-Temperature Oxidation of Propane from Synchrotron Photoionization Mass Spectrometry and Multiscale Informatics Modeling
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Intricate Internal Rotation Surface and Fundamental Infrared Transitions of the n -Propyl Radical
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Measurements, Theory, and Modeling of OH Formation in Ethyl + O ₂ and Propyl + O ₂ Reactions
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Understanding low-temperature first-stage ignition delay: Propane
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The gaseous products from the oxidation of propane at 318°C
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Molecular Structure of Propylene
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Low temperature n-butane oxidation skeletal mechanism, based on multilevel approach
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Coupled-cluster methods including noniterative corrections for quadruple excitations
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Multiscale Informatics for Low-Temperature Propane Oxidation: Further Complexities in Studies of Complex Reactions
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