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

Abstract

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.

Authors:

^[1];

^[2];

^[1]

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

Publication Date:: Mon Feb 25 00:00:00 EST 2019

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

OSTI Identifier:: 1503282

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

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 150; Journal Issue: 8; 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; astrochemistry; combustion; electronic structure methods; elementary reactions; kinetics; master equation; partition function; thermochemistry

Citation Formats


                    Nguyen, Thanh Lam, Ruscic, Branko, and Stanton, John F. A master equation simulation for the • OH + CH 3 OH reaction.  United States: N. p., 2019. 
Web.  doi:10.1063/1.5081827.

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                    Nguyen, Thanh Lam, Ruscic, Branko, & Stanton, John F. A master equation simulation for the • OH + CH 3 OH reaction.  United States.  https://doi.org/10.1063/1.5081827

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                    Nguyen, Thanh Lam, Ruscic, Branko, and Stanton, John F. Mon .  
"A master equation simulation for the • OH + CH 3 OH reaction".  United States.  https://doi.org/10.1063/1.5081827.  https://www.osti.gov/servlets/purl/1503282.

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@article{osti_1503282,

  title        = {A master equation simulation for the • OH + CH 3 OH reaction},

  author       = {Nguyen, Thanh Lam and Ruscic, Branko and Stanton, John F.},

  abstractNote = {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.},

  doi          = {10.1063/1.5081827},

  journal      = {Journal of Chemical Physics},

  number       = 8,

  volume       = 150,

  place        = {United States},

  year         = {Mon Feb 25 00:00:00 EST 2019},

  month        = {Mon Feb 25 00:00:00 EST 2019}

}

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

Abstract

Citation Formats

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 journal, November 1999

Kinetics of the reactions of the hydroxyl radical with CH3OH and C2H5OH between 235 and 360 K journal, May 2003

General contraction of Gaussian basis sets. II. Atomic natural orbitals and the calculation of atomic and molecular properties journal, January 1990

Solution of Some One- and Two-Dimensional Master Equation Models for Thermal Dissociation: The Dissociation of Methane in the Low-Pressure Limit journal, May 2002

Temperature dependence and branching ratio of the CH3OH + OH reaction journal, April 1984

A shock tube study of CH 3 OH + OH → Products using OH laser absorption journal, January 2015

Hydrogen-atom abstraction from methanol by hydroxyl radical journal, March 1989

Kinetics of the reactions of HO with methanol (210–351 K) and with ethanol (216–368 K) journal, January 2005

Rate Constants and CH3O Product Yield of the Reaction OH + CH3OH → Products journal, November 1983

Stabilization of the Simplest Criegee Intermediate from the Reaction between Ozone and Ethylene: A High-Level Quantum Chemical and Kinetic Analysis of Ozonolysis journal, May 2015

Variational unimolecular rate theory journal, July 1983

Introduction to Active Thermochemical Tables: Several “Key” Enthalpies of Formation Revisited † journal, November 2004

Kinetics of the reaction of OH radicals with CH3OH and CD3OD studied by laser photolysis coupled to high repetition rate laser induced fluorescence journal, April 2009

The gas phase reactions of hydroxyl radicals with a series of aliphatic alcohols over the temperature range 240-440 K journal, November 1987

Semiclassical Transition-State Theory Based on Fourth-Order Vibrational Perturbation Theory: The Symmetrical Eckart Barrier journal, June 2016

A Steady-State Approximation to the Two-Dimensional Master Equation for Chemical Kinetics Calculations journal, February 2015

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Low Temperature Kinetics of the CH 3 OH + OH Reaction journal, April 2014

13 C, 18 O, and D Fractionation Effects in the Reactions of CH 3 OH Isotopologues with Cl and OH Radicals journal, November 2008

Current Status of Transition-State Theory journal, January 1996

Predictive a priori pressure-dependent kinetics journal, December 2014

Ab Initio Reaction Rate Constants Computed Using Semiclassical Transition-State Theory: HO + H 2 → H 2 O + H and Isotopologues journal, May 2011

Methanol oxidation in a flow reactor: Implications for the branching ratio of the CH3OH+OH reaction journal, January 2008

Application of inverse iteration to 2‐dimensional master equations journal, June 1997

Theoretical Study of the Kinetics of the Hydrogen Abstraction from Methanol. 3. Reaction of Methanol with Hydrogen Atom, Methyl, and Hydroxyl Radicals journal, May 1999

A practical implementation of semi-classical transition state theory for polyatomics journal, October 2010

Methanol dimer formation drastically enhances hydrogen abstraction from methanol by OH at low temperature journal, January 2016

Unified statistical model for ’’complex’’ and ’’direct’’ reaction mechanisms journal, September 1976

HEAT: High accuracy extrapolated ab initio thermochemistry journal, December 2004

High-accuracy extrapolated ab initio thermochemistry. II. Minor improvements to the protocol and a vital simplification journal, August 2006

Reaction of HO with CO: Tunneling Is Indeed Important journal, May 2012

The Rate-Constant of the Reaction of Hydroxyl Radicals With Methanol, Ethanol and (D3)Methanol journal, January 1986

On the Quantum Mechanics of the Rotational Distortion of Multiplets in Molecular Spectra journal, August 1928

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

Theoretical study on the kinetics for OH reactions with CH3OH and C2H5OH journal, January 2007

Accelerated chemistry in the reaction between the hydroxyl radical and methanol at interstellar temperatures facilitated by tunnelling journal, June 2013

Semiclassical transition state theory. A new perspective journal, October 1993

Active Thermochemical Tables: thermochemistry for the 21st century journal, January 2005

Methylhydroxycarbene: Tunneling Control of a Chemical Reaction journal, June 2011

Theoretical Study of Reaction of Ketene with Water in the Gas Phase: Formation of Acetic Acid? journal, October 2013

Communication: Thermal unimolecular decomposition of syn-CH 3 CHOO: A kinetic study journal, October 2016

Kinetic studies of the reactions of atomic fluorine and hydroxyl radical with methanol journal, February 1989

The importance of OH radical–neutral low temperature tunnelling reactions in interstellar clouds using a new model journal, May 2014

Three-Dimensional Master Equation (3DME) Approach journal, August 2018

High-accuracy extrapolated ab initio thermochemistry. III. Additional improvements and overview journal, March 2008

Variational Transition State Theory journal, October 1984

Kinetics of the Methanol Reaction with OH at Interstellar, Atmospheric, and Combustion Temperatures journal, February 2018

REACTIVITY OF OH AND CH 3 OH BETWEEN 22 AND 64 K: MODELING THE GAS PHASE PRODUCTION OF CH 3 O IN BARNARD 1b journal, May 2016

Active Thermochemical Tables: Sequential Bond Dissociation Enthalpies of Methane, Ethane, and Methanol and the Related Thermochemistry journal, February 2015

Evaluated Kinetic Data for Combustion Modeling: Supplement II journal, September 2005

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 journal, January 2018

Full Iterative Solution of the Two-Dimensional Master Equation for Thermal Unimolecular Reactions journal, January 1996

Current status of transition-state theory journal, July 1983

Current status of transition-state theory journal, December 1983

Reactivity of OH and CH3OH between 22 and 64 K: Modelling the gas phase production of CH3O in Barnard 1b text, January 2016

Computational kinetics of the hydrogen abstraction reactions of n -propanol and iso-propanol by OH radical journal, January 2019

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

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
journal, November 1999

Kinetics of the reactions of the hydroxyl radical with CH3OH and C2H5OH between 235 and 360 K
journal, May 2003

General contraction of Gaussian basis sets. II. Atomic natural orbitals and the calculation of atomic and molecular properties
journal, January 1990

Solution of Some One- and Two-Dimensional Master Equation Models for Thermal Dissociation: The Dissociation of Methane in the Low-Pressure Limit
journal, May 2002

Temperature dependence and branching ratio of the CH3OH + OH reaction
journal, April 1984

A shock tube study of CH 3 OH + OH → Products using OH laser absorption
journal, January 2015

Hydrogen-atom abstraction from methanol by hydroxyl radical
journal, March 1989

Kinetics of the reactions of HO with methanol (210–351 K) and with ethanol (216–368 K)
journal, January 2005

Rate Constants and CH3O Product Yield of the Reaction OH + CH3OH → Products
journal, November 1983

Stabilization of the Simplest Criegee Intermediate from the Reaction between Ozone and Ethylene: A High-Level Quantum Chemical and Kinetic Analysis of Ozonolysis
journal, May 2015

Variational unimolecular rate theory
journal, July 1983

Introduction to Active Thermochemical Tables: Several “Key” Enthalpies of Formation Revisited ^†
journal, November 2004

Kinetics of the reaction of OH radicals with CH3OH and CD3OD studied by laser photolysis coupled to high repetition rate laser induced fluorescence
journal, April 2009

The gas phase reactions of hydroxyl radicals with a series of aliphatic alcohols over the temperature range 240-440 K
journal, November 1987

Semiclassical Transition-State Theory Based on Fourth-Order Vibrational Perturbation Theory: The Symmetrical Eckart Barrier
journal, June 2016

A Steady-State Approximation to the Two-Dimensional Master Equation for Chemical Kinetics Calculations
journal, February 2015

Unimolecular Reaction of Methyl Isocyanide to Acetonitrile: A High-Level Theoretical Study
journal, April 2018

Low Temperature Kinetics of the CH ₃ OH + OH Reaction
journal, April 2014

¹³ C, ¹⁸ O, and D Fractionation Effects in the Reactions of CH ₃ OH Isotopologues with Cl and OH Radicals
journal, November 2008

Current Status of Transition-State Theory
journal, January 1996

Predictive a priori pressure-dependent kinetics
journal, December 2014

Ab Initio Reaction Rate Constants Computed Using Semiclassical Transition-State Theory: HO + H ₂ → H ₂ O + H and Isotopologues
journal, May 2011

Methanol oxidation in a flow reactor: Implications for the branching ratio of the CH3OH+OH reaction
journal, January 2008

Application of inverse iteration to 2‐dimensional master equations
journal, June 1997

Theoretical Study of the Kinetics of the Hydrogen Abstraction from Methanol. 3. Reaction of Methanol with Hydrogen Atom, Methyl, and Hydroxyl Radicals
journal, May 1999

A practical implementation of semi-classical transition state theory for polyatomics
journal, October 2010

Methanol dimer formation drastically enhances hydrogen abstraction from methanol by OH at low temperature
journal, January 2016

Unified statistical model for ’’complex’’ and ’’direct’’ reaction mechanisms
journal, September 1976

HEAT: High accuracy extrapolated ab initio thermochemistry
journal, December 2004

High-accuracy extrapolated ab initio thermochemistry. II. Minor improvements to the protocol and a vital simplification
journal, August 2006

Reaction of HO with CO: Tunneling Is Indeed Important
journal, May 2012

The Rate-Constant of the Reaction of Hydroxyl Radicals With Methanol, Ethanol and (D3)Methanol
journal, January 1986

On the Quantum Mechanics of the Rotational Distortion of Multiplets in Molecular Spectra
journal, August 1928

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

Theoretical study on the kinetics for OH reactions with CH3OH and C2H5OH
journal, January 2007

Accelerated chemistry in the reaction between the hydroxyl radical and methanol at interstellar temperatures facilitated by tunnelling
journal, June 2013

Semiclassical transition state theory. A new perspective
journal, October 1993

Active Thermochemical Tables: thermochemistry for the 21st century
journal, January 2005

Methylhydroxycarbene: Tunneling Control of a Chemical Reaction
journal, June 2011

Theoretical Study of Reaction of Ketene with Water in the Gas Phase: Formation of Acetic Acid?
journal, October 2013

Communication: Thermal unimolecular decomposition of syn-CH ₃ CHOO: A kinetic study
journal, October 2016

Kinetic studies of the reactions of atomic fluorine and hydroxyl radical with methanol
journal, February 1989

The importance of OH radical–neutral low temperature tunnelling reactions in interstellar clouds using a new model
journal, May 2014

Three-Dimensional Master Equation (3DME) Approach
journal, August 2018

High-accuracy extrapolated ab initio thermochemistry. III. Additional improvements and overview
journal, March 2008

Variational Transition State Theory
journal, October 1984

Kinetics of the Methanol Reaction with OH at Interstellar, Atmospheric, and Combustion Temperatures
journal, February 2018

REACTIVITY OF OH AND CH ₃ OH BETWEEN 22 AND 64 K: MODELING THE GAS PHASE PRODUCTION OF CH ₃ O IN BARNARD 1b
journal, May 2016

Active Thermochemical Tables: Sequential Bond Dissociation Enthalpies of Methane, Ethane, and Methanol and the Related Thermochemistry
journal, February 2015

Evaluated Kinetic Data for Combustion Modeling: Supplement II
journal, September 2005

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
journal, January 2018

Full Iterative Solution of the Two-Dimensional Master Equation for Thermal Unimolecular Reactions
journal, January 1996

Current status of transition-state theory
journal, July 1983

Current status of transition-state theory
journal, December 1983

Reactivity of OH and CH3OH between 22 and 64 K: Modelling the gas phase production of CH3O in Barnard 1b
text, January 2016

Computational kinetics of the hydrogen abstraction reactions of n -propanol and iso-propanol by OH radical
journal, January 2019