The CH(X2Π) + H2O reaction: two transition state kinetics

Nguyen, Thanh Lam; Peeters, Jozef

doi:10.1039/d1cp02234b

Title: The CH(X²Π) + H₂O reaction: two transition state kinetics

Journal Article · Fri Jul 16 00:00:00 EDT 2021 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/d1cp02234b· OSTI ID:1852518

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^[2]

Univ. of Florida, Gainesville, FL (United States)
Univ. of Leuven, Celestijnenlaan, Heverlee (Belgium)

he reaction of ground state methylidyne (CH) with water vapor (H₂O) is theoretically re-investigated using high-level coupled cluster computations in combination with semi-classical transition state theory (SCTST) and two-dimensional master equation simulations. Insertion of CH into a H–O bond of H₂O over a submerged barrier via a well-skipping mechanism yielding solely H and CH₂O is characterized. The reaction kinetics is effectively determined by the formation of a pre-reaction van der Waals complex (PRC, HC—OH₂) and its subsequent isomerization to activated CH₂OH in competition with PRC re-dissociation. The tunneling effects are found to be minor, while variational effects in the PRC → CH₂OH step are negligible. The calculated rate coefficient k(T) is nearly pressure-independent, but strongly depends on temperature with pronounced down-up behavior: a high value of 2 x 10^-10 cm³ s^-1 at 50 K, followed by a fairly steep decrease down to 8 × 10^-12 cm³ s^-1 at 900 K, but increasing again to 5 × 10^-11 cm³ s^-1 at 3500 K. Over the T-range of this work, k(T) can be expressed as: k(T, P = 0) = 2.31 × 10^-11 (T/300 K)^-1.615 exp(-38.45/T) cm³ s^-1 for T = 50-400 K k(T, P = 0) = 1.15 × 10^-12 (T/300 K)^0.8637 exp(892.6/T) cm³ s^-1 for T = 400-1000 K k(T, P = 0) = 4.57 × 10^-15 (T/300 K)^3.375 exp(3477.4/T) cm³ s^-1 for T = 1000–3500 K.

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Research Organization:: Univ. of Florida, Gainesville, FL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0018164

OSTI ID:: 1852518

Alternate ID(s):: OSTI ID: 1809871

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 23, Issue 30; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (55)

Unravelling combustion mechanisms through a quantitative understanding of elementary reactions Miller, James A.; Pilling, Michael J.; Troe, Jürgen Proceedings of the Combustion Institute, Vol. 30, Issue 1 https://doi.org/10.1016/j.proci.2004.08.281	journal	January 2005
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
Production of chemi-ions and formation of CH and CH2 radicals in methane-oxygen and ethylene-oxygen flames Peeters, Jozef; Vinckier, Christiaan Symposium (International) on Combustion, Vol. 15, Issue 1 https://doi.org/10.1016/S0082-0784(75)80362-6	journal	January 1975
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
Quantum anharmonic densities of states using the Wang–Landau method Basire, M.; Parneix, P.; Calvo, F. The Journal of Chemical Physics, Vol. 129, Issue 8 https://doi.org/10.1063/1.2965905	journal	August 2008
Theory of thermal unimolecular reactions at low pressures. I. Solutions of the master equation Troe, J. The Journal of Chemical Physics, Vol. 66, Issue 11 https://doi.org/10.1063/1.433837	journal	June 1977
Coupled-cluster techniques for computational chemistry: The CFOUR program package Matthews, Devin A.; Cheng, Lan; Harding, Michael E. The Journal of Chemical Physics, Vol. 152, Issue 21 https://doi.org/10.1063/5.0004837	journal	June 2020
Kinetics and mechanisms of the reaction of CH with H2O Bergeat, Astrid; Moisan, Sandy; Méreau, Raphaël Chemical Physics Letters, Vol. 480, Issue 1-3 https://doi.org/10.1016/j.cplett.2009.07.080	journal	September 2009
Some applications of the transition state method to the calculation of reaction velocities, especially in solution Evans, M. G.; Polanyi, M. Transactions of the Faraday Society, Vol. 31 https://doi.org/10.1039/tf9353100875	journal	January 1935
A Theoretical Study on the Dynamics of the Reaction of CH Radicals with Water Mazarei, Elham; Mousavipour, S. Hosein The Journal of Physical Chemistry A, Vol. 121, Issue 42 https://doi.org/10.1021/acs.jpca.7b05504	journal	October 2017
High-accuracy extrapolated ab initio thermochemistry. IV. A modified recipe for computational efficiency Thorpe, James H.; Lopez, Chris A.; Nguyen, Thanh Lam The Journal of Chemical Physics, Vol. 150, Issue 22 https://doi.org/10.1063/1.5095937	journal	June 2019
Improved method for calculating projected frequencies along a reaction path Baboul, Anwar G.; Schlegel, H. Bernhard The Journal of Chemical Physics, Vol. 107, Issue 22 https://doi.org/10.1063/1.475238	journal	December 1997
Determining the density of states for classical statistical models: A random walk algorithm to produce a flat histogram Wang, Fugao; Landau, D. P. Physical Review E, Vol. 64, Issue 5 https://doi.org/10.1103/PhysRevE.64.056101	journal	October 2001
An ab initio study on the insertion reactions of CH [ X ² II] with NH ₃ , H ₂ O, and HF Wang, Zhi-Xiang; Liu, Ruo-Zhuang; Huang, Ming-Bao Canadian Journal of Chemistry, Vol. 74, Issue 6 https://doi.org/10.1139/v96-100	journal	June 1996
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen Dunning, Thom H. The Journal of Chemical Physics, Vol. 90, Issue 2 https://doi.org/10.1063/1.456153	journal	January 1989
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
Experimental Studies of Gas-Phase Reactivity in Relation to Complex Organic Molecules in Star-Forming Regions Cooke, Ilsa R.; Sims, Ian R. ACS Earth and Space Chemistry, Vol. 3, Issue 7 https://doi.org/10.1021/acsearthspacechem.9b00064	journal	May 2019
Variational unimolecular rate theory Hase, William L. Accounts of Chemical Research, Vol. 16, Issue 7 https://doi.org/10.1021/ar00091a004	journal	July 1983
Empirical Equations to Calculate 16 of the Transport Collision Integrals Ω ^{( l, s )*} for the Lennard‐Jones (12–6) Potential Neufeld, Philip D.; Janzen, A. R.; Aziz, R. A. The Journal of Chemical Physics, Vol. 57, Issue 3 https://doi.org/10.1063/1.1678363	journal	August 1972
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
Complete Basis Set ab Initio Study of the CH Insertion Reaction with Water, Ammonia, and Hydrogen Fluoride Jursic, Branko S. The Journal of Physical Chemistry A, Vol. 102, Issue 46 https://doi.org/10.1021/jp981587v	journal	November 1998
The UMIST database for astrochemistry 2012 McElroy, D.; Walsh, C.; Markwick, A. J. Astronomy & Astrophysics, Vol. 550 https://doi.org/10.1051/0004-6361/201220465	journal	January 2013
Efficient, Multiple-Range Random Walk Algorithm to Calculate the Density of States Wang, Fugao; Landau, D. P. Physical Review Letters, Vol. 86, Issue 10 https://doi.org/10.1103/PhysRevLett.86.2050	journal	March 2001
The Polanyi Lecture. The colourful world of complex-forming bimolecular reactions Troe, J. Journal of the Chemical Society, Faraday Transactions, Vol. 90, Issue 16 https://doi.org/10.1039/ft9949002303	journal	January 1994
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
A Two Transition State Model for Radical−Molecule Reactions: A Case Study of the Addition of OH to C ₂ H ₄ Greenwald, Erin E.; North, Simon W.; Georgievskii, Yuri The Journal of Physical Chemistry A, Vol. 109, Issue 27 https://doi.org/10.1021/jp058041a	journal	July 2005
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
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
Mechanism of “prompt” no formation in hydrocarbon flames Blauwens, Joanna; Smets, Bruno; Peeters, Jozef Symposium (International) on Combustion, Vol. 16, Issue 1 https://doi.org/10.1016/S0082-0784(77)80395-0	journal	January 1977
Tunneling corrections to unimolecular rate constants, with application to formaldehyde Miller, William H. Journal of the American Chemical Society, Vol. 101, Issue 23 https://doi.org/10.1021/ja00517a004	journal	November 1979
Unusual Low-Temperature Reactivity of Water: The CH + H ₂ O Reaction as a Source of Interstellar Formaldehyde? Hickson, Kevin M.; Caubet, Philippe; Loison, Jean-Christophe The Journal of Physical Chemistry Letters, Vol. 4, Issue 17 https://doi.org/10.1021/jz401425f	journal	August 2013
Reduced dimensionality theory of quantum reactive scattering Bowman, Joel M. The Journal of Physical Chemistry, Vol. 95, Issue 13 https://doi.org/10.1021/j100166a014	journal	June 1991
Why CCSD(T) works: a different perspective Stanton, John F. Chemical Physics Letters, Vol. 281, Issue 1-3 https://doi.org/10.1016/S0009-2614(97)01144-5	journal	December 1997
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
Identification of the CH + O ₂ → OH(A) + CO Reaction as the Source of OH(A−X) Chemiluminescence in C ₂ H ₂ /O/H/O ₂ Atomic Flames and Determination of Its Absolute Rate Constant over the Range T = 296 to 511 K Carl, S. A.; Van Poppel, M.; Peeters, J. The Journal of Physical Chemistry A, Vol. 107, Issue 50 https://doi.org/10.1021/jp035568j	journal	December 2003
A master equation simulation for the ^• OH + CH ₃ OH reaction Nguyen, Thanh Lam; Ruscic, Branko; Stanton, John F. The Journal of Chemical Physics, Vol. 150, Issue 8 https://doi.org/10.1063/1.5081827	journal	February 2019
Predictive Theory for Hydrogen Atom−Hydrocarbon Radical Association Kinetics Harding, Lawrence B.; Georgievskii, Yuri; Klippenstein, Stephen J. The Journal of Physical Chemistry A, Vol. 109, Issue 21 https://doi.org/10.1021/jp0508608	journal	June 2005
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
Ab Initio Thermal Rate Calculations of HO + HO = O( ³ P) + H ₂ O Reaction and Isotopologues Nguyen, Thanh Lam; Stanton, John F. The Journal of Physical Chemistry A, Vol. 117, Issue 13 https://doi.org/10.1021/jp312246q	journal	February 2013
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
Reaction of CH with H ₂ O: Temperature Dependence and Isotope Effect Blitz, Mark A.; Pesa, Michèle; Pilling, Michael J. The Journal of Physical Chemistry A, Vol. 103, Issue 29 https://doi.org/10.1021/jp9903716	journal	July 1999
Quantum mechanical investigation of the O+H2→OH+H reaction Balakrishnan, N. The Journal of Chemical Physics, Vol. 119, Issue 1 https://doi.org/10.1063/1.1576532	journal	July 2003
The Activated Complex in Chemical Reactions Eyring, Henry The Journal of Chemical Physics, Vol. 3, Issue 2 https://doi.org/10.1063/1.1749604	journal	February 1935
Adiabatic Rotations in Unimolecular Rate Theory Forst, W. The Journal of Chemical Physics, Vol. 48, Issue 8 https://doi.org/10.1063/1.1669667	journal	April 1968
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
Pragmatic Solution for a Fully E , J -Resolved Master Equation Nguyen, Thanh Lam; Stanton, John F. The Journal of Physical Chemistry A, Vol. 124, Issue 15 https://doi.org/10.1021/acs.jpca.9b11379	journal	March 2020
Sums and Densities of Fully Coupled Anharmonic Vibrational States: A Comparison of Three Practical Methods Nguyen, Thanh Lam; Barker, John R. The Journal of Physical Chemistry A, Vol. 114, Issue 10 https://doi.org/10.1021/jp100132s	journal	February 2010
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
Pressure-Dependent Rate Constant Caused by Tunneling Effects: OH + HNO ₃ as an Example Nguyen, Thanh Lam; Stanton, John F. The Journal of Physical Chemistry Letters, Vol. 11, Issue 9 https://doi.org/10.1021/acs.jpclett.0c00733	journal	April 2020
Kinetic study of the reaction CH( X ² Π)+H ₂ ⇄CH ₂ ( X ³ B ₁ )+H in the temperature range 372 to 675 K Zabarnick, S.; Fleming, J. W.; Lin, M. C. The Journal of Chemical Physics, Vol. 85, Issue 8 https://doi.org/10.1063/1.451808	journal	October 1986
An efficient linear-scaling CCSD(T) method based on local natural orbitals Rolik, Zoltán; Szegedy, Lóránt; Ladjánszki, István The Journal of Chemical Physics, Vol. 139, Issue 9 https://doi.org/10.1063/1.4819401	journal	September 2013
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
Development and assessment of new exchange-correlation functionals Hamprecht, Fred A.; Cohen, Aron J.; Tozer, David J. The Journal of Chemical Physics, Vol. 109, Issue 15 https://doi.org/10.1063/1.477267	journal	October 1998
Diffusion approximations of the two-dimensional master equation Robertson, S. H.; Pilling, M. J.; Green, N. J. B. Molecular Physics, Vol. 89, Issue 5 https://doi.org/10.1080/00268979609482556	journal	December 1996
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

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Title: The CH(X²Π) + H₂O reaction: two transition state kinetics