skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.5017305· OSTI ID:1540155
 [1];  [1];  [2];  [1];  [1]
  1. Univ. of Georgia, Athens, GA (United States). Dept. of Chemistry, Center for Computational Chemistry
  2. Northwest A&F Univ., Shaanxi (China). College of Chemistry & Pharmacy
+ Show Author Affiliations

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.

Research Organization:
Univ. of Georgia, Athens, GA (United States); Univ. of California, Oakland, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
SC0018412; AC02-05CH11231; SC0015512
OSTI ID:
1540155
Alternate ID(s):
OSTI ID: 1423507
Journal Information:
Journal of Chemical Physics, Vol. 148, Issue 9; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 14 works
Citation information provided by
Web of Science

References (110)

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
Investigating the ground-state rotamers of n-propylperoxy radical journal November 2016
Infrared Frequency-Modulation Probing of Product Formation in Alkyl + O 2 Reactions:  II. The Reaction of C 3 H 7 with O 2 between 296 and 683 K journal April 2001
The C 2 H 5 + O 2 Reaction Mechanism:  High-Level ab Initio Characterizations journal November 2000
From theoretical reaction dynamics to chemical modeling of combustion journal January 2017
A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples 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
Progress toward a unified detailed kinetic model for the autoignition of alkanes from C4 to C10 between 600 and 1200 K journal July 2005
Wave function continuity and the diagonal Born-Oppenheimer correction at conical intersections journal May 2016
Model Identity S N 2 Reactions CH 3 X + X - (X = F, Cl, CN, OH, SH, NH 2 , PH 2 ):  Marcus Theory Analyzed 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
Self-Consistent Field Theory for Open Shells of Electronic Systems 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
In pursuit of the ab initio limit for conformational energy prototypes journal June 1998
Cysteine conformations revisited journal May 2007
Ab initio total atomization energies of small molecules — towards the basis set limit journal September 1996
Molecular structure of oxetane journal July 1975
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
A reduced reaction mechanism for the combustion of n-butane journal January 2017
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions journal May 1992
Measurements and Automated Mechanism Generation Modeling of OH Production in Photolytically Initiated Oxidation of the Neopentyl Radical ‖ journal May 2007
Arrhenius parameters for the reaction i-C3H7+ O2? C3H6+ HO2 journal January 1988
New Insights into Low-Temperature Oxidation of Propane from Synchrotron Photoionization Mass Spectrometry and Multiscale Informatics Modeling journal February 2015
Intricate Internal Rotation Surface and Fundamental Infrared Transitions of the n -Propyl Radical journal July 2014
Measurements, Theory, and Modeling of OH Formation in Ethyl + O 2 and Propyl + O 2 Reactions journal June 2003
Understanding low-temperature first-stage ignition delay: Propane journal October 2015
The gaseous products from the oxidation of propane at 318°C journal January 1960
Molecular Structure of Propylene journal October 1961
Low temperature n-butane oxidation skeletal mechanism, based on multilevel approach journal April 2010
Coupled-cluster methods including noniterative corrections for quadruple excitations journal August 2005
Multiscale Informatics for Low-Temperature Propane Oxidation: Further Complexities in Studies of Complex Reactions journal February 2015
Addition of C 3 H 8 to slowly reacting mixtures of hydrogen and oxygen at 480°C journal January 1970
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
The extrapolation of one-electron basis sets in electronic structure calculations: How it should work and how it can be made to work journal January 2005
Restricted open‐shell Hartree–Fock‐based many‐body perturbation theory: Theory and application of energy and gradient calculations journal November 1992
General atomic and molecular electronic structure system journal November 1993
Open‐shell coupled‐cluster theory journal June 1993
Gaussian basis sets for use in correlated molecular calculations. V. Core‐valence basis sets for boron through neon journal September 1995
Improvement of the Modeling of the Low-Temperature Oxidation of n -Butane: Study of the Primary Reactions journal February 2012
The puckering inversion barrier and vibrational spectrum of cyclopentene. A scaled quantum mechanical force field algorithm journal August 1992
New experiments and validated master-equation modeling for OH production in propyl+O2 reactions journal January 2011
Effects of Olefin Group and Its Position on the Kinetics for Intramolecular H-Shift and HO 2 Elimination of Alkenyl Peroxy Radicals journal February 2011
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
A diagnostic for determining the quality of single-reference electron correlation methods journal April 1989
On the ab initio determination of higher‐order force constants at nonstationary reference geometries journal February 1993
Predicting chemical kinetics with computational chemistry: is QOOH→HOQO important in fuel ignition? journal February 2004
PSI3: An open-source Ab Initio electronic structure package : PSI3: An Open-Source journal April 2007
Conformers of Gaseous Serine journal July 2016
On the Correlation Problem in Atomic and Molecular Systems. Calculation of Wavefunction Components in Ursell‐Type Expansion Using Quantum‐Field Theoretical Methods journal December 1966
Basis-set convergence of correlated calculations on water journal June 1997
Thermodynamic Properties and Kinetic Parameters for Cyclic Ether Formation from Hydroperoxyalkyl Radicals journal June 2003
An efficient linear-scaling CCSD(T) method based on local natural orbitals journal September 2013
The fate of the tert-butyl radical in low-temperature autoignition reactions journal May 2017
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal January 1988
From the Time-Dependent, Multiple-Well Master Equation to Phenomenological Rate Coefficients journal October 2002
Spectroscopy from Space journal January 2014
Measurements, Theory, and Modeling of OH Formation in Ethyl + O 2 and Propyl + O 2 Reactions journal August 2004
Molecular Spectra and Molecular Structure journal November 1929
Spectroscopy from Space journal January 1984
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density text January 1988
Molecular Spectra and Molecular Structure journal October 1929
Comment on: "Estimating the Hartree-Fock limit from finite basis set calculations" [Jensen F (2005) Theor Chem Acc 113:267] text January 2005

Cited By (3)

High-level theoretical characterization of the vinoxy radical ( • CH 2 CHO) + O 2 reaction journal May 2018
Riddles of the structure and vibrational dynamics of HO 3 resolved near the ab initio limit journal September 2019
Characterization of the 2-methylvinoxy radical + O 2 reaction: A focal point analysis and composite multireference study journal September 2019

Similar Records

Pericyclic reaction benchmarks: hierarchical computations targeting CCSDT(Q)/CBS and analysis of DFT performance
Journal Article · Wed Aug 03 00:00:00 EDT 2022 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:1540155
+5 more
Investigating the Ground-State Rotamers of n-Propylperoxy Radical
Journal Article · Tue Nov 01 00:00:00 EDT 2016 · Journal of Chemical Physics · OSTI ID:1540155
The water trimer reaction OH + (H2O)3 → (H2O)2OH + H2O
Journal Article · Tue Apr 21 00:00:00 EDT 2020 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:1540155
+3 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry
Physics