Reaction CH<sub>3</sub> + OH Studied over the 294–714 K Temperature and 1–100 bar Pressure Ranges

Sangwan, Manuvesh; Чесноков, Е. Н.; Krasnoperov, Lev N.

doi:10.1021/jp305070c

Cited by 27 publications

(51 citation statements)

References 54 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The apparent cross sections obtained at 216.56 nm were reported previously (Supporting Information for ref 13). This is the wavelength that corresponds to the maximum of the Q+P peak in the double-peaked absorption spectrum of methyl radical at room temperature.…”

Section: ■ Resultssupporting

confidence: 72%

See 1 more Smart Citation

Reaction CH₃ + CH₃ → C₂H₆ Studied over the 292–714 K Temperature and 1–100 bar Pressure Ranges

et al. 2015

Self Cite

View full text Add to dashboard Cite

Reaction of recombination of methyl radicals, CH3 + CH3 → C2H6 (1) was studied using pulsed laser photolysis coupled to transient UV-vis absorption spectroscopy over the 292-714 K temperature and 1-100 bar pressure ranges (bath gas He), very close to the high-pressure limit. Methyl radicals were produced by photolysis of acetone at 193.3 nm or in the reaction of electronically excited oxygen atoms O((1)D), produced in the photolysis of N2O at 193.3 nm, with CH4, and subsequent reaction of OH with CH4. Temporal profiles of CH3 were recorded via absorption at 216.36 and 216.56 nm using a xenon arc lamp and a spectrograph. The absolute intensity of the photolysis light inside the reactor was determined by an accurate in situ actinometry based on the ozone formation in photolysis of N2O/O2/N2 mixtures. The rate constant of reaction 1 in the high-pressure limit has a negative temperature dependence: k1,inf = (5.66 ± 0.43) × 10(-11)(T/298 K)(-0.37) cm(3) molecule(-1) s(-1) (292-714 K).

show abstract

Section: ■ Resultssupporting

confidence: 72%

“…1 Precise knowledge of the kinetic parameters of reaction 1 is nessassary in laboratory studies of other reactions involving methyl radicals. 12, 13 In relative kinetic studies involving methyl radicals, reaction 1 was frequently used as a reference reaction.…”

Section: ■ Introductionmentioning

confidence: 99%

Reaction CH₃ + CH₃ → C₂H₆ Studied over the 292–714 K Temperature and 1–100 bar Pressure Ranges

et al. 2015

Self Cite

View full text Add to dashboard Cite

show abstract

“…Email: jmbowma@emory.edu temperatures and pressures for several decades. Recent work can be found in [18][19][20][21][22][23][24]. Methanol is also widely found in the interstellar medium and its mechanism of formation is still a subject of discussion [25].…”

Section: Introductionmentioning

confidence: 99%

Full-dimensional, ab initio potential energy surface for CH₃OH → CH₃+OH

Bowman

2013

Molecular Physics

View full text Add to dashboard Cite

An accurate, ab initio potential energy surface (PES) is reported for CH 3 OH including the bound region as well as the barrierless dissociation to CH 3 + OH. The surface is a linear least-squares fit to a total of 45,199 ab initio energies, most of which were computed using CCSD(T)-F12b/aug-cc-pVDZ theory and a small number using CASPT2/aug-cc-pVDZ theory. The latter set was done in the multi-reference region of the PES in order to obtain a realistic description of the OH-CH 3 interaction in the near asymptotic region. The geometries and harmonic frequencies of the stationary points agree very well with direct CCSD(T)-F12b calculations. The three-fold barrier to internal rotation of CH 3 OH is also accurately described by the PES. The zero-point energies of methanol and CH 3 + OH are determined by Diffusion Monte Carlo calculations. The D 0 dissociation energy is 90.1 kcal/mol, in very good agreement with the recent IUPAC evaluation [Ruscic et al., J. Phys. Chem. Ref. Data 34, 573 (2005)] result of 90.25 kcal/mol. Keywords: potential energy surface; ab initio; methanol dissociation energy IntroductionThe rovibrational spectroscopy of methanol has been the subject of numerous experimental [1-8] and theoretical papers [9-17], with a focus on the facile internal torsional motion. Signatures of that motion in the vibrational spectrum of the fundamentals and overtones of the CH and OHstretch modes have been reported in recent experiments.Methanol is a challenging system for an ab initio approach, owing both to the dimensionality of the configuration space (12 vibrational degrees of freedom) and also the need to accurately describe the low-barrier torsional motion. High-level theoretical work on the vibration/torsion energies of CH 3 OH has made use of ab initio-based force fields and a potential that are limited to the region of the minimum of the potential [11][12][13][14][15][16][17]. The most recent of these [15] used electronic energies obtained using coupled-clustersingles-doubles and perturbative treatment of triples excitations (CCSD(T)) theory with large polarised basis sets, i.e. aug-cc-pVTZ. The limited PES we developed [15] was a fit to 19,315 CCSD(T)/aVTZ energies. That PES was used in MULTIMODE-Reaction Path calculations [15,16] of numerous low-lying vibration/torsion energies, which are in good agreement with experiment.That PES does not describe dissociation or near dissociation to any fragments, in particular to CH 3 + OH. These are among the dominant products of the thermal decomposition of CH 3 OH. That decomposition as well as the recombination of CH 3 + OH are important processes in combustion chemistry and have been studied over a range of

show abstract

“…Email: nguyenhuutho04@gmail.com https://doi.org/10.25073/2588-1140/vnunst.4763 mạnh nhưng gốc CH 3 lại phân hủy rất ít [3,4]. Gần đây, những nghiên cứu về phản ứng của gốc methyl với nhiều loại phân tử khác nhau như CH 3 OH, C 2 H 5 OH, C 2 H 2 , C 2 H 4 , C 2 H 6 , H 2 CO, OH…đã được thực hiện nhưng các nghiên cứu về phản ứng của gốc methyl với ethylamine còn ít được quan tâm [5][6][7][8][9][10].…”

Section: đặT Vấn đề unclassified

Theoretical Study on Reaction Pathways of Methyl Radical with Ethylamine

Tho¹,

Sang²

2018

NST

View full text Add to dashboard Cite

The mechanisms for the reaction of methyl radical with ethylamine were determined by the density functional theory using the atomic structures of the reactants, transition states and products optimized at the B3LYP/6-311++G(3df,2p) level of theory. Seven transition states were identified for the production of CH3CHNH2 + CH4 (TS1), CH3CH2NH + CH4 (TS2), CH2CH2NH2 + CH4 (TS3), CH3CH2NHCH3 + H (TS4), CH3CH2 + CH3NH2 (TS5), C2H6 + CH2NH2 (TS6) and C3H8 + NH2 (TS7) with the corresponding barriers, 9.34, 9.90, 13.46, 27.70, 39.12, 45.82 and 69.34 kcal/mol. Thermodynamics analysis and potential energy surface showed that H-abstraction pathways take place easier than NH2-, CH3–abstractions, H-substitution of the NH2 group and CH3-substitution in ethylamine. The H-abstraction in methylene group of ethylamine is the most favourable on the PES of this reaction system. Keywords Methyl, Ethylamine, B3LYP, Transition states References [1] Lobo, V., et al., Free radicals, antioxidants and functional foods: Impact on human health. Pharmacognosy Reviews, 2010. 4(8): p. 118-126.[2] Phaniendra, A., D.B. Jestadi, and L. Periyasamy, Free Radicals: Properties, Sources, Targets, and Their Implication in Various Diseases. Indian Journal of Clinical Biochemistry, 2015. 30(1): p. 11-26.[3] Slagle, I.R., D. Sarzynski, and D. Gutman, Kinetics of the reaction between methyl radicals and oxygen atoms between 294 and 900 K. The Journal of Physical Chemistry, 1987. 91(16): p. 4375-4379.[4] Rutz L., B.H., Bozzelli J. W., Methyl Radical and Shift Reactions with Aliphatic and Aromatic Hydrocarbons: Thermochemical Properties, Reaction Paths and Kinetic Parameters. American Chemical Society, Division Fuel Chemistry, 2004. 49(1): p. 451-452.[5] Peukert, S.L. and J.V. Michael, High-Temperature Shock Tube and Modeling Studies on the Reactions of Methanol with D-Atoms and CH3-Radicals. The Journal of Physical Chemistry A, 2013. 117(40): p. 10186-10195.[6] Poutsma, M.L., Extension of Structure–Reactivity Correlations for the Hydrogen Abstraction Reaction to the Methyl Radical and Comparison to the Chlorine Atom, Bromine Atom, and Hydroxyl Radical. The Journal of Physical Chemistry A, 2016. 120(26): p. 4447-4454.[7] Shi, J., et al., Kinetic mechanisms of hydrogen abstraction reactions from methanol by methyl, triplet methylene and formyl radicals. Computational and Theoretical Chemistry, 2015. 1074: p. 73-82.[8] Peukert, S.L., et al., Direct Measurements of Rate Constants for the Reactions of CH3 Radicals with C2H6, C2H4, and C2H2 at High Temperatures. The Journal of Physical Chemistry A, 2013. 117(40): p. 10228-10238.[9] Sangwan, M., E.N. Chesnokov, and L.N. Krasnoperov, Reaction CH3 + OH Studied over the 294–714 K Temperature and 1–100 bar Pressure Ranges. The Journal of Physical Chemistry A, 2012. 116(34): p. 8661-8670.[10] Tho, N.H. and N.X. Sang, Theoretical study of the addition and hydrogen abstraction reactions of methyl radical with formaldehyde and hydroxymethylene. Journal of the Serbian Chemical Society, 2018. 83: p. 10.[11] Carl, S.A. and J.N. Crowley, Sequential Two (Blue) Photon Absorption by NO2 in the Presence of H2 as a Source of OH in Pulsed Photolysis Kinetic Studies: Rate Constants for Reaction of OH with CH3NH2, (CH3)2NH, (CH3)3N, and C2H5NH2 at 295 K. The Journal of Physical Chemistry A, 1998. 102(42): p. 8131-8141.[12] Gray, P. and A. Jones, Methyl radical reactions with ethylamine and deuterated ethylamines. Transactions of the Faraday Society, 1966. 62(0): p. 112-119.[13] Brinton, R.K. and D.H. Volman, Decomposition of Di‐t‐butyl Peroxide and Kinetics of the Gas Phase Reaction of t‐butoxy Radicals in the Presence of Ethylenimine. The Journal of Chemical Physics, 1952. 20(1): p. 25-28.[14] Brinton, R.K., The abstraction of hydrogen atoms from amines and related compounds. Canadian Journal of Chemistry, 1960. 38(8): p. 1339-1345.[15] M. J. Frisch, G.W.T., H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, G. A. Petersson, H. Nakatsuji, X. Li, M. Caricato, A. Marenich, J. Bloino, B. G. Janesko, R. Gomperts, B. Mennucci, H. P. Hratchian, J. V. Ortiz, A. F. Izmaylov, J. L. Sonnenberg, D. Williams-Young, F. Ding, F. Lipparini, F. Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D. Ranasinghe, V. G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, K. Throssell, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, J. M. Millam, M. Klene, C. Adamo, R. Cammi, J. W. Ochterski, R. L. Martin, K. Morokuma, O. Farkas, J. B. Foresman, and D. J. Fox, Gaussian 09, Revision C.01. Gaussian, Inc., Wallingford CT., 2010.[16] Hatipoglu, A., et al., Photo-oxidative degradation of toluene in aqueous media by hydroxyl radicals. Journal of Photochemistry and Photobiology A: Chemistry, 2010. 215(1): p. 59-68.[17] Eren, B. and Y. Yalcin Gurkan, Possible reaction pathways of the lincomycin molecule according to the DFT calculation method. 2017, 2017. 82(3): p. 11.[18] Becke, A.D., Density‐functional thermochemistry. II. The effect of the Perdew–Wang generalized‐gradient correlation correction. The Journal of Chemical Physics, 1992. 97(12): p. 9173-9177.[19] Becke, A.D., Density‐functional thermochemistry. I. The effect of the exchange‐only gradient correction. The Journal of Chemical Physics, 1992. 96(3): p. 2155-2160.[20] Becke, A.D., Density‐functional thermochemistry. III. The role of exact exchange. The Journal of Chemical Physics, 1993. 98(7): p. 5648-5652.[21] Yang, W., R.G. Parr, and C. Lee, Various functionals for the kinetic energy density of an atom or molecule. Physical Review A, 1986. 34(6): p. 4586-4590.[22] Hehre W. , R.L., Schleyer P. V. R. , and Pople J. A., Ab Initio Molecular Orbital Theory. 1986, New York: Wiley.[23] Andersson, M.P. and P. Uvdal, New Scale Factors for Harmonic Vibrational Frequencies Using the B3LYP Density Functional Method with the Triple-ζ Basis Set 6-311+G(d,p). The Journal of Physical Chemistry A, 2005. 109(12): p. 2937-2941.[24] Herzberg, G., Electronic spectra and electronic structure of polyatomic molecules, 1966, Van Nostrand: New York.[25] Sverdlov L.M., K.M.A., Krainov E. P., Vibrational Spectra of Polyatomic Molecules, 1974, Wiley: New York.[26] Hirota, E., Anharmonic potential function and equilibrium structure of methane. Journal of Molecular Spectroscopy, 1979. 77(2): p. 213-221.[27] Kuchitsu, K., Structure of Free Polyatomic Molecules. 1998: Springer-Verlag Berlin Heidelberg.[28] Hamada, Y., et al., Molecular structural of the gauche and trans conformers of ethylamine as studies by gas electron diffraction. Journal of Molecular Structure, 1986. 146: p. 253-262.[29] Goos, E.B., A.; Ruscic, B., Extended Third Millennium Ideal Gas and Condensed Phase Thermochemical Database for Combustion with Updates from Active Thermochemical Tables. http://garfield.chem.elte.hu/Burcat/burcat.html, March, 2018.

show abstract

Reaction CH₃ + OH Studied over the 294–714 K Temperature and 1–100 bar Pressure Ranges

Cited by 27 publications

References 54 publications

Reaction CH₃ + CH₃ → C₂H₆ Studied over the 292–714 K Temperature and 1–100 bar Pressure Ranges

Reaction CH₃ + CH₃ → C₂H₆ Studied over the 292–714 K Temperature and 1–100 bar Pressure Ranges

Full-dimensional, ab initio potential energy surface for CH₃OH → CH₃+OH

Theoretical Study on Reaction Pathways of Methyl Radical with Ethylamine

Contact Info

Product

Resources

About

Reaction CH3 + OH Studied over the 294–714 K Temperature and 1–100 bar Pressure Ranges

Cited by 27 publications

References 54 publications

Reaction CH3 + CH3 → C2H6 Studied over the 292–714 K Temperature and 1–100 bar Pressure Ranges

Reaction CH3 + CH3 → C2H6 Studied over the 292–714 K Temperature and 1–100 bar Pressure Ranges

Full-dimensional, ab initio potential energy surface for CH3OH → CH3+OH

Theoretical Study on Reaction Pathways of Methyl Radical with Ethylamine

Contact Info

Product

Resources

About

Reaction CH₃ + OH Studied over the 294–714 K Temperature and 1–100 bar Pressure Ranges

Reaction CH₃ + CH₃ → C₂H₆ Studied over the 292–714 K Temperature and 1–100 bar Pressure Ranges

Reaction CH₃ + CH₃ → C₂H₆ Studied over the 292–714 K Temperature and 1–100 bar Pressure Ranges

Full-dimensional, ab initio potential energy surface for CH₃OH → CH₃+OH