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

被引：4

作者：

Mackie, Iain D. ^{[1
,2
]}

DiLabio, Gino A. ^{[1
,2
]}

机构：

[1] Natl Res Council Canada, Natl Inst Nanotechnol, Edmonton, AB T6G 2M9, Canada

[2] Univ Alberta, Dept Phys, Edmonton, AB T6G 2G7, Canada

来源：

ORGANIC & BIOMOLECULAR CHEMISTRY | 2011年 / 9卷 / 09期

关键词：

SELF-DIRECTED GROWTH; DISPERSION CORRECTIONS; RATE CONSTANTS; M06; SUITE; AB-INITIO; CYCLOPROPYLCARBINYL; THERMOCHEMISTRY; NANOSTRUCTURES; APPROXIMATION; ENERGIES;

D O I：

10.1039/c0ob01246g

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The 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 alpha-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.

引用

收藏

页码：3158 / 3164

页数：7

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