Intramolecular hydrogen migration in Alkylperoxy and Hydroperoxyalkylperoxy radicals: Accurate treatment of hindered rotors
Name
Green_Intramolecular hydrogen.pdf
Size
330.38 KB
Format
Adobe PDF
Checksum (MD5)
9f1a312a01f0ab6f3bac2a615248d863
Author(s)
Sharma, Sandeep
Raman, Sumathy
Green, William H.
Date Issued
2009
Journal
Journal of Physical Chemistry A
Publisher
American Chemical Society
Citation
Sharma, Sandeep, Sumathy Raman, and William H. Green. “Intramolecular Hydrogen Migration in Alkylperoxy and Hydroperoxyalkylperoxy Radicals: Accurate Treatment of Hindered Rotors.” The Journal of Physical Chemistry A 114.18 (2010): 5689-5701.
Version
Author's final manuscript
Abstract
We have calculated the thermochemistry and rate coefficients for stable molecules
and reactions in the title reaction families using CBS-QB3 and B3LYP/CBSB7
methods. The accurate treatment of hindered rotors for molecules having multi-
ple internal rotors with potentials that are not independent of each other can be
problematic and a simplified scheme is suggested to treat them. This is particu-
larly important for hydroperoxyalkylperoxy radicals (HOOQOO). Two new ther-
mochemical group values are suggested in this paper and with these values the
group additivity method for calculation of enthalpy as implemented in RMG gives
good agreement with CBS-QB3 predictions. The barrier heights follow the Evans-
Polanyi relationship for each type of intramolecular hydrogen migration reaction
studied.
MIT Department
Massachusetts Institute of Technology. Department of Chemical Engineering
Terms of Use
Creative Commons Attribution-Noncommercial-Share Alike
Persistent DSpace Link
DOI of Published Version
http://dx.doi.org/10.1021/jp9098792
https://doi.org/10.1021/jp9098792
