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Title: 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:
 [1];  [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Florida, Gainesville, FL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. 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.
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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
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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.
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@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}
}
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https://doi.org/10.1021/acs.jpclett.8b01259
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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
  • DOI: 10.1021/ja00881a006

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
  • DOI: 10.1021/j100881a018

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
  • DOI: 10.1021/j100711a002

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
  • DOI: 10.1021/j100602a002

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
  • DOI: 10.1063/1.1734509

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
  • DOI: 10.1139/v76-339

Intracavity cw dye laser photoactivation of unimolecular reactants: isomerization of state-selected methyl isocyanide
journal, November 1977

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
  • DOI: 10.1021/j150489a013

Unimolecular Dissociations and Free Radical Recombination Reactions
journal, March 1952

  • Marcus, R. A.
  • The Journal of Chemical Physics, Vol. 20, Issue 3
  • DOI: 10.1063/1.1700424

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
  • DOI: 10.1063/1.1678107

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
  • DOI: 10.1021/ja00770a005

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
  • DOI: 10.1063/1.436568

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
  • DOI: 10.1021/ja00531a009

Density functional theory and ab initio study of CH3NC and HNC isomerization
journal, June 1996

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
  • DOI: 10.1021/ed083p69

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
  • DOI: 10.1063/1.1680672

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
  • DOI: 10.1063/1.1811608

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
  • DOI: 10.1063/1.2206789

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
  • DOI: 10.1063/1.2835612

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
  • DOI: 10.1021/acs.jpca.5b00997

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
  • DOI: 10.1021/acs.jpca.5b02088

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
  • DOI: 10.1063/1.4964393

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
  • DOI: 10.1021/jp2022743

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

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
  • DOI: 10.1016/0009-2614(90)87217-F

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

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
  • DOI: 10.1021/jp047912y

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
  • DOI: 10.1088/1742-6596/16/1/078

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
  • DOI: 10.1063/1.1724828

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
  • DOI: 10.1007/s00214-013-1415-z

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
  • DOI: 10.1021/acs.jpca.7b06017

A fifth-order perturbation comparison of electron correlation theories
journal, May 1989

Non-iterative fifth-order triple and quadruple excitation energy corrections in correlated methods
journal, February 1990

Anharmonic force constant calculations
journal, December 1972

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
  • DOI: 10.1063/1.458458

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
  • DOI: 10.1063/1.451917

Quantitative analysis of Fermi resonances by harmonic derivatives of perturbation theory corrections
journal, October 2009

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
  • DOI: 10.1021/jp3051033

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
  • DOI: 10.1021/jp0556512

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
  • DOI: 10.1002/kin.1017

Comparison of models for calculating the RRKM unimolecular rate constant k(E, J)
journal, November 1990

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
  • DOI: 10.1021/jp972581t

Some Recent Advances and Remaining Questions Regarding Unimolecular Rate Theory
journal, October 1998

  • Hase, William L.
  • Accounts of Chemical Research, Vol. 31, Issue 10
  • DOI: 10.1021/ar970156c

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
  • DOI: 10.1021/jp014689l

The Activated Complex in Chemical Reactions
journal, February 1935

  • Eyring, Henry
  • The Journal of Chemical Physics, Vol. 3, Issue 2
  • DOI: 10.1063/1.1749604

Some applications of the transition state method to the calculation of reaction velocities, especially in solution
journal, January 1935

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
  • DOI: 10.1021/jp953748q

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
  • DOI: 10.1063/1.433837

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
  • DOI: 10.1063/1.433838

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
  • DOI: 10.1063/1.451770

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
  • DOI: 10.1021/jp0144698

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
  • DOI: 10.1021/jp062693x

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
  • DOI: 10.1021/jp953430y

Time evolution in the unimolecular master equation at low temperatures: full spectral solution with scalable iterative methods and high precision
journal, November 2001

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
  • DOI: 10.1063/1.473656
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    journal, June 2019

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    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
    • DOI: 10.1063/1.5081827

    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
    • DOI: 10.1039/c9cp04310a

    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
    • DOI: 10.1063/1.5126805
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