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

Nguyen, Thanh Lam; Thorpe, James H.; Bross, David H.; Ruscic, Branko; Stanton, John F.

doi:10.1021/acs.jpclett.8b01259

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

Journal Article · Thu Apr 26 00:00:00 EDT 2018 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.8b01259· OSTI ID:1461519

Nguyen, Thanh Lam ^[1]; Thorpe, James H. ^[1]; ^[2]; ^[3]; ^[1]

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)

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)).

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; Air Force Research Laboratory (AFRL) - Air Force Office of Scientific Research (AFOSR)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1461519

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 10 Vol. 9; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Is CH ₃ NC isomerization an intrinsic non-RRKM unimolecular reaction? Jayee, Bhumika; Malpathak, Shreyas; Ma, Xinyou The Journal of Chemical Physics, Vol. 151, Issue 18 https://doi.org/10.1063/1.5126805	journal	November 2019

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