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

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...

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Bibliographic Details
Published in:The journal of physical chemistry letters 2018-05, Vol.9 (10), p.2532-2538
Main Authors: Nguyen, Thanh Lam, Thorpe, James H, Bross, David H, Ruscic, Branko, Stanton, John F
Format: Article
Language:English
Subjects:
Active Thermochemical Tables
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Summary: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)).
ISSN:1948-7185
1948-7185
DOI:10.1021/acs.jpclett.8b01259