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Unimolecular Reaction of Methyl Isocyanide to Acetonitrile: A High-Level Theoretical Study
Thanh Lam Nguyen1, James H Thorpe1, David H Bross2
1Quantum Theory Project, Department of Chemistry and Physics , University of Florida , Gainesville , Florida 32611 , United States.
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)).
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