Ring-opening radical clock reactions: Many density functionals have difficulty keeping time

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DOIResolve DOI: http://doi.org/10.1039/c0ob01246g
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TypeArticle
Journal titleOrganic and Biomolecular Chemistry
ISSN1477-0520
Volume9
Issue9
Pages31583164; # of pages: 7
SubjectCyclopropyl; Density functionals; Functionals; Radical clocks; Ring opening; Ring opening reaction; Density functional theory
AbstractThe ability of several density-functional theory methods to describe the kinetics and energetics of a series of ring-opening reactions of cyclopropyl and cyclobutyl-type radicals was explored. PBE, B971 and B3LYP perform quite well in their ability to replicate experiment, based upon the ring opening of cyclopropylcarbinyl, two α-trialkylsilyloxycyclopropylmethyl radicals, pentamethylcyclopropylcarbinyl, cyclobutylcarbinyl and 1- cyclobutylethylcarbinyl. The other functionals tested, which includes BLYP, CAM-B3LYP, BHandHLYP, B2PLYP and B2PLYP-D, as well as functionals designed for kinetics applications, namely MPW1K, BMK and M06-2X, all perform poorly. The latter of these functionals display some integration grid dependencies. © 2011 The Royal Society of Chemistry.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC); National Institute for Nanotechnology (NINT-INNT)
Peer reviewedYes
NPARC number21271488
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Record identifier14c4982c-c4c2-4d44-80e1-25d02e8fd848
Record created2014-03-24
Record modified2016-05-09
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