Seemingly simple stereoelectronic effects in alkane isomers and the implications for Kohn-Sham density functional theory

被引：350

作者：

Grimme, Stefan ^{[1
]}

机构：

[1] Univ Munster, Organ Chem Inst, D-48149 Munster, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2006年 / 45卷 / 27期

关键词：

ab initio calculations; alkanes; density functional calculations; isomerization; stereoelectronic effects;

D O I：

10.1002/anie.200600448

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

(Figure Presented) A theoretical disaster: In contrast to general opinion, modern density functional methods are not able to even qualitatively describe the overall energetics of simple alkylation reactions (see scheme). The main reason is that the currently used hybrid functionals almost completely neglect the generally relevant electron correlation effects for medium-range electron-electron distances. © 2006 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

页码：4460 / 4464

页数：5

共 35 条

[1] ELECTRONIC-STRUCTURE CALCULATIONS ON WORKSTATION COMPUTERS - THE PROGRAM SYSTEM TURBOMOLE
AHLRICHS, R
BAR, M
HASER, M
HORN, H
KOLMEL, C
[J]. CHEMICAL PHYSICS LETTERS, 1989, 162 (03) : 165 - 169
[2] AHLRICHS R, 2003, TURBOMOLE VERSION 5
[3] The torsional conformations of butane: Definitive energetics from ab initio methods
Allinger, NL
Fermann, JT
Allen, WD
Schaefer, HF
[J]. JOURNAL OF CHEMICAL PHYSICS, 1997, 106 (12) : 5143 - 5150
[4] MOLECULAR MECHANICS - THE MM3 FORCE-FIELD FOR HYDROCARBONS .1.
ALLINGER, NL
YUH, YH
LII, JH
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (23) : 8551 - 8566
[5] A NEW MIXING OF HARTREE-FOCK AND LOCAL DENSITY-FUNCTIONAL THEORIES
BECKE, AD
[J]. JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (02) : 1372 - 1377
[6] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE
BECKE, AD
[J]. JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) : 5648 - 5652
[7] DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR
BECKE, AD
[J]. PHYSICAL REVIEW A, 1988, 38 (06): : 3098 - 3100
[8] Progressive systematic underestimation of reaction energies by the B3LYP model as the number of C-C bonds increases: Why organic chemists should use multiple DFT models for calculations involving polycarbon hydrocarbons
Check, CE
Gilbert, TM
[J]. JOURNAL OF ORGANIC CHEMISTRY, 2005, 70 (24) : 9828 - 9834
[9] Assessment of Gaussian-3 and density functional theories for a larger experimental test set
Curtiss, LA
Raghavachari, K
Redfern, PC
Pople, JA
[J]. JOURNAL OF CHEMICAL PHYSICS, 2000, 112 (17) : 7374 - 7383
[10] DELONGCHAMPS P, 1983, ORGANIC CHEM SERIES, V1, P5

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