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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]
  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.
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}
}

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Cited by: 14 works
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Works referencing / citing this record:

High-accuracy extrapolated ab initio thermochemistry. IV. A modified recipe for computational efficiency
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A master equation simulation for the OH + CH 3 OH reaction
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