Unimolecular Reaction of Methyl Isocyanide to Acetonitrile: A High-Level Theoretical Study

Nguyen, Thanh Lam; Thorpe, James H.; Bross, David H.; Ruscic, Branko; Stanton, John F.

doi:10.1021/acs.jpclett.8b01259

Unimolecular Reaction of Methyl Isocyanide to Acetonitrile: A High-Level Theoretical Study

Journal Article · Thu Apr 26 00:00:00 EDT 2018 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.8b01259· OSTI ID:1461519

Nguyen, Thanh Lam ^[1]; Thorpe, James H. ^[1]; ^[2]; ^[3]; ^[1]

Univ. of Florida, Gainesville, FL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Chicago, IL (United States)

A combination of high-level coupled-cluster calculations and two-dimensional master equation approaches based on semiclassical transition state theory is used to reinvestigate the classic prototype unimolecular isomerization of methyl isocyanide (CH₃NC) to acetonitrile (CH₃CN). The activation energy, reaction enthalpy, and fundamental vibrational frequencies calculated from first-principles agree well with experimental results. In addition, the calculated thermal rate constants adequately reproduce those of experiment over a large range of temperature and pressure in the falloff region, where experimental results are available, and are generally consistent with statistical chemical kinetics theory (such as Rice-Ramsperger-Kassel-Marcus (RRKM) and transition state theory (TST)).

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: Air Force Research Laboratory (AFRL) - Air Force Office of Scientific Research (AFOSR); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1461519

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 10 Vol. 9; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (62)

Multiple-Well, multiple-path unimolecular reaction systems. I. MultiWell computer program suite Barker, John R. International Journal of Chemical Kinetics, Vol. 33, Issue 4 https://doi.org/10.1002/kin.1017	journal	January 2001
Active Thermochemical Tables: dissociation energies of several homonuclear first-row diatomics and related thermochemical values Ruscic, Branko; Feller, David; Peterson, Kirk A. Theoretical Chemistry Accounts, Vol. 133, Issue 1 https://doi.org/10.1007/s00214-013-1415-z	journal	November 2013
Intracavity cw dye laser photoactivation of unimolecular reactants: isomerization of state-selected methyl isocyanide Reddy, K. V.; Berry, M. J. Chemical Physics Letters, Vol. 52, Issue 1 https://doi.org/10.1016/0009-2614(77)85131-2	journal	November 1977
Comparison of models for calculating the RRKM unimolecular rate constant k(E, J) Zhu, Ling; Hase, William L. Chemical Physics Letters, Vol. 175, Issue 1-2 https://doi.org/10.1016/0009-2614(90)85528-K	journal	November 1990
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
Ab initio calculation of anharmonic constants for a transition state, with application to semiclassical transition state tunneling probabilities Miller, William H.; Hernandez, Rigoberto; Handy, Nicholas C. Chemical Physics Letters, Vol. 172, Issue 1 https://doi.org/10.1016/0009-2614(90)87217-F	journal	August 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
Density functional theory and ab initio study of CH3NC and HNC isomerization Jursic, Branko S. Chemical Physics Letters, Vol. 256, Issue 1-2 https://doi.org/10.1016/0009-2614(96)00407-1	journal	June 1996
Monte Carlo calculations on unimolecular reactions, energy transfer, and IR-multiphoton decomposition Barker, John R. Chemical Physics, Vol. 77, Issue 2 https://doi.org/10.1016/0301-0104(83)85087-3	journal	June 1983
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 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
Time evolution in the unimolecular master equation at low temperatures: full spectral solution with scalable iterative methods and high precision Frankcombe, Terry J.; Smith, Sean C. Computer Physics Communications, Vol. 141, Issue 1 https://doi.org/10.1016/S0010-4655(01)00298-3	journal	November 2001
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
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
Enthalpy of Formation of N ₂ H ₄ (Hydrazine) Revisited Feller, David; Bross, David H.; Ruscic, Branko The Journal of Physical Chemistry A, Vol. 121, Issue 32 https://doi.org/10.1021/acs.jpca.7b06017	journal	August 2017
Some Recent Advances and Remaining Questions Regarding Unimolecular Rate Theory Hase, William L. Accounts of Chemical Research, Vol. 31, Issue 10 https://doi.org/10.1021/ar970156c	journal	October 1998
Computational Studies of Chemical Reactions: The HNC–HCN and CH3NC–CH3CN Isomerizations Halpern, Arthur M. Journal of Chemical Education, Vol. 83, Issue 1 https://doi.org/10.1021/ed083p69	journal	January 2006
Comparison of models for treating angular momentum in RRKM calculations with vibrator transition states: pressure and temperature dependence of chlorine atom + acetylene association Zhu, Ling; Chen, Wei; Hase, William L. The Journal of Physical Chemistry, Vol. 97, Issue 2 https://doi.org/10.1021/j100104a010	journal	January 1993
Fall-off behavior of a thermal unimolecular system in the presence of a weak collider inert bath gas Wang, F. M.; Rabinovitch, B. S. The Journal of Physical Chemistry, Vol. 78, Issue 9 https://doi.org/10.1021/j100602a002	journal	April 1974
Energy transfer in thermal methyl isocyanide isomerization. Comprehensive investigation Chan, Siu C.; Rabinovitch, Benton S.; Bryant, James T. The Journal of Physical Chemistry, Vol. 74, Issue 17 https://doi.org/10.1021/j100711a002	journal	August 1970
Energy Transfer in Thermal Methyl Isocyanide Isomerization. Experimental Survey ¹ Fletcher, F. J.; Rabinovitch, B. S.; Watkins, K. W. The Journal of Physical Chemistry, Vol. 70, Issue 9 https://doi.org/10.1021/j100881a018	journal	September 1966
The Kinetics of the Recombination of Methyl Radicals and Iodine Atoms. Marcus, R. A.; Rice, O. K. The Journal of Physical Chemistry, Vol. 55, Issue 6 https://doi.org/10.1021/j150489a013	journal	June 1951
Transition state vibrational analysis for the methyl isocyanide rearrangement, CH3NC .fwdarw. CH3CN Saxe, Paul; Yamaguchi, Yukio; Pulay, Peter Journal of the American Chemical Society, Vol. 102, Issue 11 https://doi.org/10.1021/ja00531a009	journal	May 1980
Theoretical reaction coordinate for the methyl isocyanide isomerization Liskow, Dean H.; Bender, Charles F.; Schaefer, Henry F. Journal of the American Chemical Society, Vol. 94, Issue 15 https://doi.org/10.1021/ja00770a005	journal	July 1972
The Thermal Unimolecular Isomerization of Methyl Isocyanide. Fall-of Behaviour Schneider, F. W.; Rabinovitch, B. S. Journal of the American Chemical Society, Vol. 84, Issue 22 https://doi.org/10.1021/ja00881a006	journal	November 1962
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
Relationship between Mode Specific and Thermal Unimolecular Rate Constants for HOCl → OH + Cl Dissociation Song, Kihyung; Sun, Lipeng; Hase, William L. The Journal of Physical Chemistry A, Vol. 106, Issue 36 https://doi.org/10.1021/jp014689l	journal	June 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
Constraining the Mechanism and Kinetics of OH + NO ₂ and HO ₂ + NO Using the Multiple-Well Master Equation ^† Zhang, Jieyuan; Donahue, Neil M. The Journal of Physical Chemistry A, Vol. 110, Issue 21 https://doi.org/10.1021/jp0556512	journal	June 2006
Master Equation Methods in Gas Phase Chemical Kinetics Miller, James A.; Klippenstein, Stephen J. The Journal of Physical Chemistry A, Vol. 110, Issue 36 https://doi.org/10.1021/jp062693x	journal	September 2006
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
MESMER: An Open-Source Master Equation Solver for Multi-Energy Well Reactions Glowacki, David R.; Liang, Chi-Hsiu; Morley, Christopher The Journal of Physical Chemistry A, Vol. 116, Issue 38 https://doi.org/10.1021/jp3051033	journal	September 2012
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
Role of State Specificity in the Temperature- and Pressure-Dependent Unimolecular Rate Constants for HO ₂ → H + O ₂ Dissociation Song, Kihyung; Hase, William L. The Journal of Physical Chemistry A, Vol. 102, Issue 8 https://doi.org/10.1021/jp972581t	journal	February 1998
Detailed Microvariational RRKM Master Equation Analysis of the Product Distribution of the C ₂ H ₂ + CH(X ² Π) Reaction over Extended Temperature and Pressure Ranges Vereecken, Luc; Peeters, Jozef The Journal of Physical Chemistry A, Vol. 103, Issue 28 https://doi.org/10.1021/jp990720w	journal	July 1999
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
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
Some Features of the CH3NC→CH3CN Potential Surface Liskow, Dean H.; Bender, Charles F.; Schaefer, Henry F. The Journal of Chemical Physics, Vol. 57, Issue 11 https://doi.org/10.1063/1.1678107	journal	December 1972
On non‐RRKM unimolecular kinetics: Molecules in general, and CH ₃ NC in particular Bunker, Don L.; Hase, W. L. The Journal of Chemical Physics, Vol. 59, Issue 9 https://doi.org/10.1063/1.1680672	journal	November 1973
Unimolecular Dissociations and Free Radical Recombination Reactions Marcus, R. A. The Journal of Chemical Physics, Vol. 20, Issue 3 https://doi.org/10.1063/1.1700424	journal	March 1952
IUPAC Critical Evaluation of Thermochemical Properties of Selected Radicals. Part I Ruscic, Branko; Boggs, James E.; Burcat, Alexander Journal of Physical and Chemical Reference Data, Vol. 34, Issue 2 https://doi.org/10.1063/1.1724828	journal	June 2005
Studies with a Single‐Pulse Shock Tube. II. The Thermal Decomposition of Perfluorocyclobutane Lifshitz, Assa; Carroll, H. F.; Bauer, S. H. The Journal of Chemical Physics, Vol. 39, Issue 7 https://doi.org/10.1063/1.1734509	journal	October 1963
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
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
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
Theory of thermal unimolecular reactions at low pressures. II. Strong collision rate constants. Applications Troe, J. The Journal of Chemical Physics, Vol. 66, Issue 11 https://doi.org/10.1063/1.433838	journal	June 1977
The unimolecular isomerization of methyl isocyanide to methyl cyanide (acetonitrile) Redmon, Lynn T.; Purvis, George D.; Bartlett, Rodney J. The Journal of Chemical Physics, Vol. 69, Issue 12 https://doi.org/10.1063/1.436568	journal	December 1978
A theoretical analysis of the overtone‐induced isomerization of methyl isocyanide Miller, James A.; Chandler, David W. The Journal of Chemical Physics, Vol. 85, Issue 8 https://doi.org/10.1063/1.451770	journal	October 1986
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
Stochastic simulation of chemically activated unimolecular reactions Vereecken, Luc; Huyberechts, Guido; Peeters, Jozef The Journal of Chemical Physics, Vol. 106, Issue 16 https://doi.org/10.1063/1.473656	journal	April 1997
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
Quantitative analysis of Fermi resonances by harmonic derivatives of perturbation theory corrections Matthews, Devin; Stanton, John Molecular Physics, Vol. 107, Issue 3 https://doi.org/10.1080/00268970902769463	journal	October 2009
Calculation of fundamental frequencies for small polyatomic molecules: a comparison between correlation consistent and atomic natural orbital basis sets McCaslin, Laura; Stanton, John Molecular Physics, Vol. 111, Issue 9-11 https://doi.org/10.1080/00268976.2013.811303	journal	May 2013
Anharmonic force constant calculations Hoy, A. R.; Mills, I. M.; Strey, G. Molecular Physics, Vol. 24, Issue 6 https://doi.org/10.1080/00268977200102361	journal	December 1972
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
The thermal isomerisation of methyl isocyanide in the temperature range 120–320 °C Collister, John Lewis; Pritchard, Huw Owen Canadian Journal of Chemistry, Vol. 54, Issue 15 https://doi.org/10.1139/v76-339	journal	August 1976

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Is CH ₃ NC isomerization an intrinsic non-RRKM unimolecular reaction? Jayee, Bhumika; Malpathak, Shreyas; Ma, Xinyou The Journal of Chemical Physics, Vol. 151, Issue 18 https://doi.org/10.1063/1.5126805	journal	November 2019

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