A master equation simulation for the • OH + CH 3 OH reaction

Nguyen, Thanh Lam; Ruscic, Branko; Stanton, John F.

doi:10.1063/1.5081827

Title: A master equation simulation for the ^• OH + CH ₃ OH reaction

Journal Article · 24 February 2019 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/1.5081827 · OSTI ID:1503282

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Univ. of Florida, Gainesville, FL (United States)
Argonne National Laboratory (ANL),Lemont, IL (United States)

A combined (fixed-J) two-dimensional master-equation / semi-classical transition state theory / variational Rice-Ramsperger-Kassel-Marcus (2DME/SCTST/vRRKM) approach has been used to compute reaction rate coefficients of •OH with CH₃OH over a wide range of temperatures (10 - 2500 K) and pressures (10^-1-10⁴ Torr) based on a potential energy surface that has been constructed using a modification of the HEAT thermochemical protocol. The calculated results show that the title reaction is nearly pressure-independent when T > 250 K, but depends strongly on pressure at lower temperatures. Also, the preferred mechanism and rate constants are found to be very sensitive to temperature. The reaction pathway CH₃OH + ^•OH → CH₃O^• + H₂O proceeds exclusively through tunneling at exceedingly low temperatures (T ≤50 K) typical of those established in interstellar environments. In this regime, the rate constant is found to increase with decreasing temperature, which agrees with low-temperature experimental results. The thermodynamically favored reaction pathway CH₃OH + ^•OH → ^•CH₂OH + H₂O becomes dominant at higher temperatures (T ≥ 200 K), such as those found in Earth’s atmosphere as well as combustion environments. By modifying the ab initio barrier heights slightly, experimental rate constants from 200 to 1250 K can be satisfactorily reproduced.

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Research Organization:: Argonne National Laboratory (ANL), Lemont, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-06CH11357; FG02-07ER15884

OSTI ID:: 1503282

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 8 Vol. 150; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (62)

Application of inverse iteration to 2‐dimensional master equations Robertson, Struan H.; Pilling, Michael J.; Gates, Kevin E. Journal of Computational Chemistry, Vol. 18, Issue 8 https://doi.org/10.1002/(sici)1096-987x(199706)18:8<1004::aid-jcc4>3.3.co;2-a	journal	June 1997
Rate Constants and CH3O Product Yield of the Reaction OH + CH3OH → Products Hägele, J.; Lorenz, K.; Rhäsa, D. Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 87, Issue 11 https://doi.org/10.1002/bbpc.19830871112	journal	November 1983
Methanol oxidation in a flow reactor: Implications for the branching ratio of the CH3OH+OH reaction Rasmussen, Christian Lund; Wassard, Karin Hedebo; Dam-Johansen, Kim International Journal of Chemical Kinetics, Vol. 40, Issue 7 https://doi.org/10.1002/kin.20323	journal	January 2008
The gas phase reactions of hydroxyl radicals with a series of aliphatic alcohols over the temperature range 240-440 K Wallington, Timothy J.; Kurylo, Michael J. International Journal of Chemical Kinetics, Vol. 19, Issue 11 https://doi.org/10.1002/kin.550191106	journal	November 1987
Kinetics of the reaction of OH radicals with CH3OH and CD3OD studied by laser photolysis coupled to high repetition rate laser induced fluorescence Parker, Alexander; Jain, Chaithanya; Schoemaecker, Coralie Reaction Kinetics and Catalysis Letters, Vol. 96, Issue 2 https://doi.org/10.1007/s11144-009-5509-5	journal	April 2009
Temperature dependence and branching ratio of the CH3OH + OH reaction Meier, U.; Grotheer, H. H.; Just, Th. Chemical Physics Letters, Vol. 106, Issue 1-2 https://doi.org/10.1016/0009-2614(84)87019-0	journal	April 1984
Non-iterative fifth-order triple and quadruple excitation energy corrections in correlated methods Bartlett, Rodney J.; Watts, J. D.; Kucharski, S. A. Chemical Physics Letters, Vol. 165, Issue 6 https://doi.org/10.1016/0009-2614(90)87031-l	journal	February 1990
Semiclassical transition state theory. A new perspective Hernandez, Rigoberto; Miller, William H. Chemical Physics Letters, Vol. 214, Issue 2 https://doi.org/10.1016/0009-2614(93)90071-8	journal	October 1993
Vibration–Rotation Structure in Asymmetric- and Symmetric-Top Molecules Mills, Ian M. Molecular Spectroscopy https://doi.org/10.1016/B978-0-12-580640-4.50013-3	book	January 1972
A practical implementation of semi-classical transition state theory for polyatomics Nguyen, Thanh Lam; Stanton, John F.; Barker, John R. Chemical Physics Letters, Vol. 499, Issue 1-3 https://doi.org/10.1016/j.cplett.2010.09.015	journal	October 2010
Theoretical study on the kinetics for OH reactions with CH3OH and C2H5OH Xu, Shucheng; Lin, M. C. Proceedings of the Combustion Institute, Vol. 31, Issue 1 https://doi.org/10.1016/j.proci.2006.07.132	journal	January 2007
A shock tube study of CH 3 OH + OH → Products using OH laser absorption Zaczek, Luke T.; Lam, King Yiu; Davidson, David F. Proceedings of the Combustion Institute, Vol. 35, Issue 1 https://doi.org/10.1016/j.proci.2014.05.051	journal	January 2015
A fifth-order perturbation comparison of electron correlation theories Raghavachari, Krishnan; Trucks, Gary W.; Pople, John A. Chemical Physics Letters, Vol. 157, Issue 6 https://doi.org/10.1016/s0009-2614(89)87395-6	journal	May 1989
Kinetics of the reactions of the hydroxyl radical with CH3OH and C2H5OH between 235 and 360 K Jiménez, E.; Gilles, M. K.; Ravishankara, A. R. Journal of Photochemistry and Photobiology A: Chemistry, Vol. 157, Issue 2-3 https://doi.org/10.1016/s1010-6030(03)00073-x	journal	May 2003
A Steady-State Approximation to the Two-Dimensional Master Equation for Chemical Kinetics Calculations Nguyen, Thanh Lam; Stanton, John F. The Journal of Physical Chemistry A, Vol. 119, Issue 28 https://doi.org/10.1021/acs.jpca.5b00997	journal	February 2015
Active Thermochemical Tables: Sequential Bond Dissociation Enthalpies of Methane, Ethane, and Methanol and the Related Thermochemistry Ruscic, Branko The Journal of Physical Chemistry A, Vol. 119, Issue 28 https://doi.org/10.1021/acs.jpca.5b01346	journal	February 2015
Stabilization of the Simplest Criegee Intermediate from the Reaction between Ozone and Ethylene: A High-Level Quantum Chemical and Kinetic Analysis of Ozonolysis Nguyen, Thanh Lam; Lee, Hyunwoo; Matthews, Devin A. The Journal of Physical Chemistry A, Vol. 119, Issue 22 https://doi.org/10.1021/acs.jpca.5b02088	journal	May 2015
Three-Dimensional Master Equation (3DME) Approach Nguyen, Thanh Lam; Stanton, John F. The Journal of Physical Chemistry A, Vol. 122, Issue 38 https://doi.org/10.1021/acs.jpca.8b06593	journal	August 2018
Semiclassical Transition-State Theory Based on Fourth-Order Vibrational Perturbation Theory: The Symmetrical Eckart Barrier Stanton, John F. The Journal of Physical Chemistry Letters, Vol. 7, Issue 14 https://doi.org/10.1021/acs.jpclett.6b01239	journal	June 2016
Unimolecular Reaction of Methyl Isocyanide to Acetonitrile: A High-Level Theoretical Study Nguyen, Thanh Lam; Thorpe, James H.; Bross, David H. The Journal of Physical Chemistry Letters, Vol. 9, Issue 10 https://doi.org/10.1021/acs.jpclett.8b01259	journal	April 2018
Variational unimolecular rate theory Hase, William L. Accounts of Chemical Research, Vol. 16, Issue 7 https://doi.org/10.1021/ar00091a004	journal	July 1983
Current status of transition-state theory Truhlar, Donald G.; Hase, William L.; Hynes, James T. The Journal of Physical Chemistry, Vol. 87, Issue 15 https://doi.org/10.1021/j100238a003	journal	July 1983
Kinetic studies of the reactions of atomic fluorine and hydroxyl radical with methanol McCaulley, J. A.; Kelly, N.; Golde, M. F. The Journal of Physical Chemistry, Vol. 93, Issue 3 https://doi.org/10.1021/j100340a002	journal	February 1989
Hydrogen-atom abstraction from methanol by hydroxyl radical Hess, Wayne P.; Tully, Frank P. The Journal of Physical Chemistry, Vol. 93, Issue 5 https://doi.org/10.1021/j100342a049	journal	March 1989
Current status of transition-state theory Truhlar, Donald G.; Hase, William L.; Hynes, James T. The Journal of Physical Chemistry, Vol. 87, Issue 26 https://doi.org/10.1021/j150644a044	journal	December 1983
Kinetics of the Methanol Reaction with OH at Interstellar, Atmospheric, and Combustion Temperatures Gao, Lu Gem; Zheng, Jingjing; Fernández-Ramos, Antonio Journal of the American Chemical Society, Vol. 140, Issue 8 https://doi.org/10.1021/jacs.7b12773	journal	February 2018
Solution of Some One- and Two-Dimensional Master Equation Models for Thermal Dissociation: The Dissociation of Methane in the Low-Pressure Limit Miller, James A.; Klippenstein, Stephen J.; Raffy, Christophe The Journal of Physical Chemistry A, Vol. 106, Issue 19 https://doi.org/10.1021/jp0144698	journal	May 2002
Introduction to Active Thermochemical Tables: Several “Key” Enthalpies of Formation Revisited ^† Ruscic, Branko; Pinzon, Reinhardt E.; Morton, Melita L. The Journal of Physical Chemistry A, Vol. 108, Issue 45 https://doi.org/10.1021/jp047912y	journal	November 2004
Ab Initio Reaction Rate Constants Computed Using Semiclassical Transition-State Theory: HO + H ₂ → H ₂ O + H and Isotopologues Nguyen, Thanh Lam; Stanton, John F.; Barker, John R. The Journal of Physical Chemistry A, Vol. 115, Issue 20 https://doi.org/10.1021/jp2022743	journal	May 2011
Theoretical Study of Reaction of Ketene with Water in the Gas Phase: Formation of Acetic Acid? Nguyen, Thanh Lam; Xue, Bert C.; Ellison, G. Barney The Journal of Physical Chemistry A, Vol. 117, Issue 43 https://doi.org/10.1021/jp408337y	journal	October 2013
Low Temperature Kinetics of the CH ₃ OH + OH Reaction Gómez Martín, J. C.; Caravan, R. L.; Blitz, M. A. The Journal of Physical Chemistry A, Vol. 118, Issue 15 https://doi.org/10.1021/jp5002995	journal	April 2014
¹³ C, ¹⁸ O, and D Fractionation Effects in the Reactions of CH ₃ OH Isotopologues with Cl and OH Radicals Feilberg, Karen L.; Gruber-Stadler, Margret; Johnson, Matthew S. The Journal of Physical Chemistry A, Vol. 112, Issue 44 https://doi.org/10.1021/jp805643x	journal	November 2008
Full Iterative Solution of the Two-Dimensional Master Equation for Thermal Unimolecular Reactions Jeffrey, Stephen J.; Gates, Kevin E.; Smith, Sean C. The Journal of Physical Chemistry, Vol. 100, Issue 17 https://doi.org/10.1021/jp953430y	journal	January 1996
Current Status of Transition-State Theory Truhlar, Donald G.; Garrett, Bruce C.; Klippenstein, Stephen J. The Journal of Physical Chemistry, Vol. 100, Issue 31 https://doi.org/10.1021/jp953748q	journal	January 1996
Theoretical Study of the Kinetics of the Hydrogen Abstraction from Methanol. 3. Reaction of Methanol with Hydrogen Atom, Methyl, and Hydroxyl Radicals Jodkowski, Jerzy T.; Rayez, Marie-Thérèse; Rayez, Jean-Claude The Journal of Physical Chemistry A, Vol. 103, Issue 19 https://doi.org/10.1021/jp984367q	journal	May 1999
Reaction of HO with CO: Tunneling Is Indeed Important Nguyen, Thanh Lam; Xue, Bert C.; Weston, Ralph E. The Journal of Physical Chemistry Letters, Vol. 3, Issue 11 https://doi.org/10.1021/jz300443a	journal	May 2012
Accelerated chemistry in the reaction between the hydroxyl radical and methanol at interstellar temperatures facilitated by tunnelling Shannon, Robin J.; Blitz, Mark A.; Goddard, Andrew Nature Chemistry, Vol. 5, Issue 9 https://doi.org/10.1038/nchem.1692	journal	June 2013
Gas phase reactions of C ₁ –C ₄ alcohols with the OH radical: A quantum mechanical approach Galano, Annia; Alvarez-Idaboy, J. Raúl; Bravo-Pérez, Graciela Phys. Chem. Chem. Phys., Vol. 4, Issue 19 https://doi.org/10.1039/b205630e	journal	January 2002
Kinetics of the reactions of HO with methanol (210–351 K) and with ethanol (216–368 K) Dillon, T. J.; Hölscher, D.; Sivakumaran, V. Phys. Chem. Chem. Phys., Vol. 7, Issue 2 https://doi.org/10.1039/b413961e	journal	January 2005
Methanol dimer formation drastically enhances hydrogen abstraction from methanol by OH at low temperature Siebrand, Willem; Smedarchina, Zorka; Martínez-Núñez, Emilio Physical Chemistry Chemical Physics, Vol. 18, Issue 32 https://doi.org/10.1039/c6cp04173f	journal	January 2016
Comment on “Methanol dimer formation drastically enhances hydrogen abstraction from methanol by OH at low temperature” by W. Siebrand, Z. Smedarchina, E. Martínez-Núñez and A. Fernández-Ramos, Phys. Chem. Chem. Phys ., 2016, 18 , 22712 Shannon, R. J.; Gómez Martín, J. C.; Caravan, R. L. Physical Chemistry Chemical Physics, Vol. 20, Issue 12 https://doi.org/10.1039/c7cp04561a	journal	January 2018
Reply to the ‘Comment on “Methanol dimer formation drastically enhances hydrogen abstraction from methanol by OH at low temperature”’ by D. Heard, R. Shannon, J. Gomez Martin, R. Caravan, M. Blitz, J. Plane, M. Antiñolo, M. Agundez, E. Jimenez, B. Ballesteros, A. Canosa, G. El Dib, J. Albaladejo and J. Cernicharo, Phys. Chem. Chem. Phys. , 2018, 20 , DOI: 10.1039/C7CP04561A Siebrand, W.; Smedarchina, Z.; Ferro-Costas, D. Physical Chemistry Chemical Physics, Vol. 20, Issue 12 https://doi.org/10.1039/c8cp00519b	journal	January 2018
Semi-classical theory for non-separable systems:. Construction of “good” action-angle variables for reaction rate constants Miller, William H. Faraday Discuss. Chem. Soc., Vol. 62, Issue 0 https://doi.org/10.1039/dc9776200040	journal	January 1977
Evaluated Kinetic Data for Combustion Modeling: Supplement II Baulch, D. L.; Bowman, C. T.; Cobos, C. J. Journal of Physical and Chemical Reference Data, Vol. 34, Issue 3 https://doi.org/10.1063/1.1748524	journal	September 2005
HEAT: High accuracy extrapolated ab initio thermochemistry Tajti, Attila; Szalay, Péter G.; Császár, Attila G. The Journal of Chemical Physics, Vol. 121, Issue 23 https://doi.org/10.1063/1.1811608	journal	December 2004
High-accuracy extrapolated ab initio thermochemistry. II. Minor improvements to the protocol and a vital simplification Bomble, Yannick J.; Vázquez, Juana; Kállay, Mihály The Journal of Chemical Physics, Vol. 125, Issue 6 https://doi.org/10.1063/1.2206789	journal	August 2006
High-accuracy extrapolated ab initio thermochemistry. III. Additional improvements and overview Harding, Michael E.; Vázquez, Juana; Ruscic, Branko The Journal of Chemical Physics, Vol. 128, Issue 11 https://doi.org/10.1063/1.2835612	journal	March 2008
Unified statistical model for ’’complex’’ and ’’direct’’ reaction mechanisms Miller, William H. The Journal of Chemical Physics, Vol. 65, Issue 6 https://doi.org/10.1063/1.433379	journal	September 1976
General contraction of Gaussian basis sets. I. Atomic natural orbitals for first‐ and second‐row atoms Almlöf, Jan; Taylor, Peter R. The Journal of Chemical Physics, Vol. 86, Issue 7 https://doi.org/10.1063/1.451917	journal	April 1987
General contraction of Gaussian basis sets. II. Atomic natural orbitals and the calculation of atomic and molecular properties Almlöf, Jan; Taylor, Peter R. The Journal of Chemical Physics, Vol. 92, Issue 1 https://doi.org/10.1063/1.458458	journal	January 1990
Master equation analysis of intermolecular energy transfer in multiple-well, multiple-channel unimolecular reactions. II. Numerical methods and application to the mechanism of the C2H5+O2 reaction Venkatesh, Prasana K.; Dean, Anthony M.; Cohen, Morrel H. The Journal of Chemical Physics, Vol. 111, Issue 18 https://doi.org/10.1063/1.480221	journal	November 1999
Communication: Thermal unimolecular decomposition of syn-CH ₃ CHOO: A kinetic study Nguyen, Thanh Lam; McCaslin, Laura; McCarthy, Michael C. The Journal of Chemical Physics, Vol. 145, Issue 13 https://doi.org/10.1063/1.4964393	journal	October 2016
The Rate-Constant of the Reaction of Hydroxyl Radicals With Methanol, Ethanol and (D3)Methanol Greenhill, Pg; Ogrady, Bv Australian Journal of Chemistry, Vol. 39, Issue 11 https://doi.org/10.1071/ch9861775	journal	January 1986
The importance of OH radical–neutral low temperature tunnelling reactions in interstellar clouds using a new model Acharyya, K.; Herbst, E.; Caravan, R. L. Molecular Physics, Vol. 113, Issue 15-16 https://doi.org/10.1080/00268976.2015.1021729	journal	May 2014
Quantum dynamics of complex-forming bimolecular reactions Guo, H. International Reviews in Physical Chemistry, Vol. 31, Issue 1 https://doi.org/10.1080/0144235x.2011.649999	journal	January 2012
Active Thermochemical Tables: thermochemistry for the 21st century Ruscic, Branko; Pinzon, Reinhardt E.; Laszewski, Gregor von Journal of Physics: Conference Series, Vol. 16 https://doi.org/10.1088/1742-6596/16/1/078	journal	January 2005
On the Quantum Mechanics of the Rotational Distortion of Multiplets in Molecular Spectra Hill, E.; Van Vleck, J. H. Physical Review, Vol. 32, Issue 2 https://doi.org/10.1103/physrev.32.250	journal	August 1928
Methylhydroxycarbene: Tunneling Control of a Chemical Reaction Schreiner, P. R.; Reisenauer, H. P.; Ley, D. Science, Vol. 332, Issue 6035 https://doi.org/10.1126/science.1203761	journal	June 2011
Predictive a priori pressure-dependent kinetics Jasper, Ahren W.; Pelzer, Kenley M.; Miller, James A. Science, Vol. 346, Issue 6214 https://doi.org/10.1126/science.1260856	journal	December 2014
Variational Transition State Theory Truhlar, D. G.; Garrett, B. C. Annual Review of Physical Chemistry, Vol. 35, Issue 1 https://doi.org/10.1146/annurev.pc.35.100184.001111	journal	October 1984
REACTIVITY OF OH AND CH ₃ OH BETWEEN 22 AND 64 K: MODELING THE GAS PHASE PRODUCTION OF CH ₃ O IN BARNARD 1b Antiñolo, M.; Agúndez, M.; Jiménez, E. The Astrophysical Journal, Vol. 823, Issue 1 https://doi.org/10.3847/0004-637x/823/1/25	journal	May 2016
Reactivity of OH and CH3OH between 22 and 64 K: Modelling the gas phase production of CH3O in Barnard 1b Antinolo, M.; Agundez, M.; Jimenez, E. arXiv https://doi.org/10.48550/arxiv.1603.04244	text	January 2016

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Title: A master equation simulation for the • OH + CH 3 OH reaction

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Title: A master equation simulation for the ^• OH + CH ₃ OH reaction