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

Title: 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)).

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

Sponsoring Organization:: 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)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1461519

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

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 18 works

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High-accuracy extrapolated ab initio thermochemistry. IV. A modified recipe for computational efficiency Thorpe, James H.; Lopez, Chris A.; Nguyen, Thanh Lam The Journal of Chemical Physics, Vol. 150, Issue 22 https://doi.org/10.1063/1.5095937	journal	June 2019
A master equation simulation for the ^• OH + CH ₃ OH reaction Nguyen, Thanh Lam; Ruscic, Branko; Stanton, John F. The Journal of Chemical Physics, Vol. 150, Issue 8 https://doi.org/10.1063/1.5081827	journal	February 2019
Single photon ionization of methyl isocyanide and the subsequent unimolecular decomposition of its cation: experiment and theory Bellili, A.; Gouid, Z.; Gazeau, M. C. Physical Chemistry Chemical Physics, Vol. 21, Issue 47 https://doi.org/10.1039/c9cp04310a	journal	January 2019
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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