Unimolecular Reaction of Methyl Isocyanide to Acetonitrile: A High-Level Theoretical Study
Abstract
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)).
- Authors:
-
- 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)
- Publication Date:
- 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; Air Force Research Laboratory (AFRL) - Air Force Office of Scientific Research (AFOSR)
- OSTI Identifier:
- 1461519
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry Letters
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 10; Journal ID: ISSN 1948-7185
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Active Thermochemical Tables
Citation Formats
Nguyen, Thanh Lam, Thorpe, James H., Bross, David H., Ruscic, Branko, and Stanton, John F. Unimolecular Reaction of Methyl Isocyanide to Acetonitrile: A High-Level Theoretical Study. United States: N. p., 2018.
Web. doi:10.1021/acs.jpclett.8b01259.
Nguyen, Thanh Lam, Thorpe, James H., Bross, David H., Ruscic, Branko, & Stanton, John F. Unimolecular Reaction of Methyl Isocyanide to Acetonitrile: A High-Level Theoretical Study. United States. https://doi.org/10.1021/acs.jpclett.8b01259
Nguyen, Thanh Lam, Thorpe, James H., Bross, David H., Ruscic, Branko, and Stanton, John F. Thu .
"Unimolecular Reaction of Methyl Isocyanide to Acetonitrile: A High-Level Theoretical Study". United States. https://doi.org/10.1021/acs.jpclett.8b01259. https://www.osti.gov/servlets/purl/1461519.
@article{osti_1461519,
title = {Unimolecular Reaction of Methyl Isocyanide to Acetonitrile: A High-Level Theoretical Study},
author = {Nguyen, Thanh Lam and Thorpe, James H. and Bross, David H. and Ruscic, Branko and Stanton, John F.},
abstractNote = {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)).},
doi = {10.1021/acs.jpclett.8b01259},
journal = {Journal of Physical Chemistry Letters},
number = 10,
volume = 9,
place = {United States},
year = {2018},
month = {4}
}
Web of Science
Works referenced in this record:
The Thermal Unimolecular Isomerization of Methyl Isocyanide. Fall-of Behaviour
journal, November 1962
- Schneider, F. W.; Rabinovitch, B. S.
- Journal of the American Chemical Society, Vol. 84, Issue 22
Energy Transfer in Thermal Methyl Isocyanide Isomerization. Experimental Survey 1
journal, September 1966
- Fletcher, F. J.; Rabinovitch, B. S.; Watkins, K. W.
- The Journal of Physical Chemistry, Vol. 70, Issue 9
Energy transfer in thermal methyl isocyanide isomerization. Comprehensive investigation
journal, August 1970
- Chan, Siu C.; Rabinovitch, Benton S.; Bryant, James T.
- The Journal of Physical Chemistry, Vol. 74, Issue 17
Fall-off behavior of a thermal unimolecular system in the presence of a weak collider inert bath gas
journal, April 1974
- Wang, F. M.; Rabinovitch, B. S.
- The Journal of Physical Chemistry, Vol. 78, Issue 9
Studies with a Single‐Pulse Shock Tube. II. The Thermal Decomposition of Perfluorocyclobutane
journal, October 1963
- Lifshitz, Assa; Carroll, H. F.; Bauer, S. H.
- The Journal of Chemical Physics, Vol. 39, Issue 7
The thermal isomerisation of methyl isocyanide in the temperature range 120–320 °C
journal, August 1976
- Collister, John Lewis; Pritchard, Huw Owen
- Canadian Journal of Chemistry, Vol. 54, Issue 15
Intracavity cw dye laser photoactivation of unimolecular reactants: isomerization of state-selected methyl isocyanide
journal, November 1977
- Reddy, K. V.; Berry, M. J.
- Chemical Physics Letters, Vol. 52, Issue 1
The Kinetics of the Recombination of Methyl Radicals and Iodine Atoms.
journal, June 1951
- Marcus, R. A.; Rice, O. K.
- The Journal of Physical Chemistry, Vol. 55, Issue 6
Unimolecular Dissociations and Free Radical Recombination Reactions
journal, March 1952
- Marcus, R. A.
- The Journal of Chemical Physics, Vol. 20, Issue 3
Some Features of the CH3NC→CH3CN Potential Surface
journal, December 1972
- Liskow, Dean H.; Bender, Charles F.; Schaefer, Henry F.
- The Journal of Chemical Physics, Vol. 57, Issue 11
Theoretical reaction coordinate for the methyl isocyanide isomerization
journal, July 1972
- Liskow, Dean H.; Bender, Charles F.; Schaefer, Henry F.
- Journal of the American Chemical Society, Vol. 94, Issue 15
The unimolecular isomerization of methyl isocyanide to methyl cyanide (acetonitrile)
journal, December 1978
- Redmon, Lynn T.; Purvis, George D.; Bartlett, Rodney J.
- The Journal of Chemical Physics, Vol. 69, Issue 12
Transition state vibrational analysis for the methyl isocyanide rearrangement, CH3NC .fwdarw. CH3CN
journal, May 1980
- Saxe, Paul; Yamaguchi, Yukio; Pulay, Peter
- Journal of the American Chemical Society, Vol. 102, Issue 11
Density functional theory and ab initio study of CH3NC and HNC isomerization
journal, June 1996
- Jursic, Branko S.
- Chemical Physics Letters, Vol. 256, Issue 1-2
Computational Studies of Chemical Reactions: The HNC–HCN and CH3NC–CH3CN Isomerizations
journal, January 2006
- Halpern, Arthur M.
- Journal of Chemical Education, Vol. 83, Issue 1
On non‐RRKM unimolecular kinetics: Molecules in general, and CH 3 NC in particular
journal, November 1973
- Bunker, Don L.; Hase, W. L.
- The Journal of Chemical Physics, Vol. 59, Issue 9
HEAT: High accuracy extrapolated ab initio thermochemistry
journal, December 2004
- Tajti, Attila; Szalay, Péter G.; Császár, Attila G.
- The Journal of Chemical Physics, Vol. 121, Issue 23
High-accuracy extrapolated ab initio thermochemistry. II. Minor improvements to the protocol and a vital simplification
journal, August 2006
- Bomble, Yannick J.; Vázquez, Juana; Kállay, Mihály
- The Journal of Chemical Physics, Vol. 125, Issue 6
High-accuracy extrapolated ab initio thermochemistry. III. Additional improvements and overview
journal, March 2008
- Harding, Michael E.; Vázquez, Juana; Ruscic, Branko
- The Journal of Chemical Physics, Vol. 128, Issue 11
A Steady-State Approximation to the Two-Dimensional Master Equation for Chemical Kinetics Calculations
journal, February 2015
- Nguyen, Thanh Lam; Stanton, John F.
- The Journal of Physical Chemistry A, Vol. 119, Issue 28
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
- Nguyen, Thanh Lam; Lee, Hyunwoo; Matthews, Devin A.
- The Journal of Physical Chemistry A, Vol. 119, Issue 22
Communication: Thermal unimolecular decomposition of syn-CH 3 CHOO: A kinetic study
journal, October 2016
- Nguyen, Thanh Lam; McCaslin, Laura; McCarthy, Michael C.
- The Journal of Chemical Physics, Vol. 145, Issue 13
Ab Initio Reaction Rate Constants Computed Using Semiclassical Transition-State Theory: HO + H 2 → H 2 O + H and Isotopologues
journal, May 2011
- Nguyen, Thanh Lam; Stanton, John F.; Barker, John R.
- The Journal of Physical Chemistry A, Vol. 115, Issue 20
A practical implementation of semi-classical transition state theory for polyatomics
journal, October 2010
- Nguyen, Thanh Lam; Stanton, John F.; Barker, John R.
- Chemical Physics Letters, Vol. 499, Issue 1-3
Semi-classical theory for non-separable systems:. Construction of “good” action-angle variables for reaction rate constants
journal, January 1977
- Miller, William H.
- Faraday Discuss. Chem. Soc., Vol. 62, Issue 0
Ab initio calculation of anharmonic constants for a transition state, with application to semiclassical transition state tunneling probabilities
journal, August 1990
- Miller, William H.; Hernandez, Rigoberto; Handy, Nicholas C.
- Chemical Physics Letters, Vol. 172, Issue 1
Semiclassical transition state theory. A new perspective
journal, October 1993
- Hernandez, Rigoberto; Miller, William H.
- Chemical Physics Letters, Vol. 214, Issue 2
Introduction to Active Thermochemical Tables: Several “Key” Enthalpies of Formation Revisited †
journal, November 2004
- Ruscic, Branko; Pinzon, Reinhardt E.; Morton, Melita L.
- The Journal of Physical Chemistry A, Vol. 108, Issue 45
Active Thermochemical Tables: thermochemistry for the 21st century
journal, January 2005
- Ruscic, Branko; Pinzon, Reinhardt E.; Laszewski, Gregor von
- Journal of Physics: Conference Series, Vol. 16
IUPAC Critical Evaluation of Thermochemical Properties of Selected Radicals. Part I
journal, June 2005
- Ruscic, Branko; Boggs, James E.; Burcat, Alexander
- Journal of Physical and Chemical Reference Data, Vol. 34, Issue 2
Active Thermochemical Tables: Sequential Bond Dissociation Enthalpies of Methane, Ethane, and Methanol and the Related Thermochemistry
journal, February 2015
- Ruscic, Branko
- The Journal of Physical Chemistry A, Vol. 119, Issue 28
Active Thermochemical Tables: dissociation energies of several homonuclear first-row diatomics and related thermochemical values
journal, November 2013
- Ruscic, Branko; Feller, David; Peterson, Kirk A.
- Theoretical Chemistry Accounts, Vol. 133, Issue 1
Enthalpy of Formation of N 2 H 4 (Hydrazine) Revisited
journal, August 2017
- Feller, David; Bross, David H.; Ruscic, Branko
- The Journal of Physical Chemistry A, Vol. 121, Issue 32
A fifth-order perturbation comparison of electron correlation theories
journal, May 1989
- Raghavachari, Krishnan; Trucks, Gary W.; Pople, John A.
- Chemical Physics Letters, Vol. 157, Issue 6
Non-iterative fifth-order triple and quadruple excitation energy corrections in correlated methods
journal, February 1990
- Bartlett, Rodney J.; Watts, J. D.; Kucharski, S. A.
- Chemical Physics Letters, Vol. 165, Issue 6
Anharmonic force constant calculations
journal, December 1972
- Hoy, A. R.; Mills, I. M.; Strey, G.
- Molecular Physics, Vol. 24, Issue 6
General contraction of Gaussian basis sets. II. Atomic natural orbitals and the calculation of atomic and molecular properties
journal, January 1990
- Almlöf, Jan; Taylor, Peter R.
- The Journal of Chemical Physics, Vol. 92, Issue 1
General contraction of Gaussian basis sets. I. Atomic natural orbitals for first‐ and second‐row atoms
journal, April 1987
- Almlöf, Jan; Taylor, Peter R.
- The Journal of Chemical Physics, Vol. 86, Issue 7
Calculation of fundamental frequencies for small polyatomic molecules: a comparison between correlation consistent and atomic natural orbital basis sets
journal, May 2013
- McCaslin, Laura; Stanton, John
- Molecular Physics, Vol. 111, Issue 9-11
Quantitative analysis of Fermi resonances by harmonic derivatives of perturbation theory corrections
journal, October 2009
- Matthews, Devin; Stanton, John
- Molecular Physics, Vol. 107, Issue 3
MESMER: An Open-Source Master Equation Solver for Multi-Energy Well Reactions
journal, September 2012
- Glowacki, David R.; Liang, Chi-Hsiu; Morley, Christopher
- The Journal of Physical Chemistry A, Vol. 116, Issue 38
Constraining the Mechanism and Kinetics of OH + NO 2 and HO 2 + NO Using the Multiple-Well Master Equation †
journal, June 2006
- Zhang, Jieyuan; Donahue, Neil M.
- The Journal of Physical Chemistry A, Vol. 110, Issue 21
Multiple-Well, multiple-path unimolecular reaction systems. I. MultiWell computer program suite
journal, January 2001
- Barker, John R.
- International Journal of Chemical Kinetics, Vol. 33, Issue 4
Comparison of models for treating angular momentum in RRKM calculations with vibrator transition states: pressure and temperature dependence of chlorine atom + acetylene association
journal, January 1993
- Zhu, Ling; Chen, Wei; Hase, William L.
- The Journal of Physical Chemistry, Vol. 97, Issue 2
Comparison of models for calculating the RRKM unimolecular rate constant k(E, J)
journal, November 1990
- Zhu, Ling; Hase, William L.
- Chemical Physics Letters, Vol. 175, Issue 1-2
Role of State Specificity in the Temperature- and Pressure-Dependent Unimolecular Rate Constants for HO 2 → H + O 2 Dissociation
journal, February 1998
- Song, Kihyung; Hase, William L.
- The Journal of Physical Chemistry A, Vol. 102, Issue 8
Some Recent Advances and Remaining Questions Regarding Unimolecular Rate Theory
journal, October 1998
- Hase, William L.
- Accounts of Chemical Research, Vol. 31, Issue 10
Relationship between Mode Specific and Thermal Unimolecular Rate Constants for HOCl → OH + Cl Dissociation
journal, June 2002
- Song, Kihyung; Sun, Lipeng; Hase, William L.
- The Journal of Physical Chemistry A, Vol. 106, Issue 36
The Activated Complex in Chemical Reactions
journal, February 1935
- Eyring, Henry
- The Journal of Chemical Physics, Vol. 3, Issue 2
Some applications of the transition state method to the calculation of reaction velocities, especially in solution
journal, January 1935
- Evans, M. G.; Polanyi, M.
- Transactions of the Faraday Society, Vol. 31
Current Status of Transition-State Theory
journal, January 1996
- Truhlar, Donald G.; Garrett, Bruce C.; Klippenstein, Stephen J.
- The Journal of Physical Chemistry, Vol. 100, Issue 31
Theory of thermal unimolecular reactions at low pressures. I. Solutions of the master equation
journal, June 1977
- Troe, J.
- The Journal of Chemical Physics, Vol. 66, Issue 11
Theory of thermal unimolecular reactions at low pressures. II. Strong collision rate constants. Applications
journal, June 1977
- Troe, J.
- The Journal of Chemical Physics, Vol. 66, Issue 11
A theoretical analysis of the overtone‐induced isomerization of methyl isocyanide
journal, October 1986
- Miller, James A.; Chandler, David W.
- The Journal of Chemical Physics, Vol. 85, Issue 8
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
- Miller, James A.; Klippenstein, Stephen J.; Raffy, Christophe
- The Journal of Physical Chemistry A, Vol. 106, Issue 19
Master Equation Methods in Gas Phase Chemical Kinetics
journal, September 2006
- Miller, James A.; Klippenstein, Stephen J.
- The Journal of Physical Chemistry A, Vol. 110, Issue 36
Full Iterative Solution of the Two-Dimensional Master Equation for Thermal Unimolecular Reactions
journal, January 1996
- Jeffrey, Stephen J.; Gates, Kevin E.; Smith, Sean C.
- The Journal of Physical Chemistry, Vol. 100, Issue 17
Time evolution in the unimolecular master equation at low temperatures: full spectral solution with scalable iterative methods and high precision
journal, November 2001
- Frankcombe, Terry J.; Smith, Sean C.
- Computer Physics Communications, Vol. 141, Issue 1
Monte Carlo calculations on unimolecular reactions, energy transfer, and IR-multiphoton decomposition
journal, June 1983
- Barker, John R.
- Chemical Physics, Vol. 77, Issue 2
Stochastic simulation of chemically activated unimolecular reactions
journal, April 1997
- Vereecken, Luc; Huyberechts, Guido; Peeters, Jozef
- The Journal of Chemical Physics, Vol. 106, Issue 16
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
journal, July 1999
- Vereecken, Luc; Peeters, Jozef
- The Journal of Physical Chemistry A, Vol. 103, Issue 28
Works referencing / citing this record:
High-accuracy extrapolated ab initio thermochemistry. IV. A modified recipe for computational efficiency
journal, June 2019
- Thorpe, James H.; Lopez, Chris A.; Nguyen, Thanh Lam
- The Journal of Chemical Physics, Vol. 150, Issue 22
A master equation simulation for the • OH + CH 3 OH reaction
journal, February 2019
- Nguyen, Thanh Lam; Ruscic, Branko; Stanton, John F.
- The Journal of Chemical Physics, Vol. 150, Issue 8
Single photon ionization of methyl isocyanide and the subsequent unimolecular decomposition of its cation: experiment and theory
journal, January 2019
- Bellili, A.; Gouid, Z.; Gazeau, M. C.
- Physical Chemistry Chemical Physics, Vol. 21, Issue 47
Is CH 3 NC isomerization an intrinsic non-RRKM unimolecular reaction?
journal, November 2019
- Jayee, Bhumika; Malpathak, Shreyas; Ma, Xinyou
- The Journal of Chemical Physics, Vol. 151, Issue 18