The role of exchange in systematic DFT errors for some organic reactions

被引：57

作者：

Brittain, David R. B. ^{[1
]}

Lin, Ching Yeh ^{[1
]}

Gilbert, Andrew T. B. ^{[1
]}

Izgorodina, Ekaterina I. ^{[1
]}

Gill, Peter M. W. ^{[1
]}

Coote, Michelle L. ^{[1
]}

机构：

[1] Australian Natl Univ, Res Sch Chem, Canberra, ACT, Australia

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2009年 / 11卷 / 08期

基金：

澳大利亚研究理事会;

关键词：

DENSITY-FUNCTIONAL THEORY; ENERGY DIFFERENCES; POLYMERIZATION; ACCURATE; BONDS;

D O I：

10.1039/b818412g

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Serious (up to 87 kJ mol(-1)) systematic DFT errors in a series of isodesmic reactions are found to be due to the DFT exchange component, and can be largely corrected by substitution of the DFT exchange energy with the Fock exchange energy.

引用

页码：1138 / 1142

页数：5

共 23 条

[1]

BECKE AD, 1994, INT J QUANTUM CHEM, P625

[2] 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 [J].

Check, CE ;

Gilbert, TM .

JOURNAL OF ORGANIC CHEMISTRY, 2005, 70 (24) :9828-9834

[3] Limitations of current density functional theories for the description of partial pi-bond breaking [J].

Choi, CH ;

Kertesz, M ;

Karpfen, A .

CHEMICAL PHYSICS LETTERS, 1997, 276 (3-4) :266-268

[4]

CRITTENDEN DL, UNPUB

[5] Assessment of Gaussian-3 and density functional theories for a larger experimental test set [J].

Curtiss, LA ;

Raghavachari, K ;

Redfern, PC ;

Pople, JA .

JOURNAL OF CHEMICAL PHYSICS, 2000, 112 (17) :7374-7383

[6] Effect of the self-interaction error for three-electron bonds:: On the development of new exchange-correlation functionals [J].

Gräfenstein, J ;

Kraka, E ;

Cremer, D .

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2004, 6 (06) :1096-1112

[7] Stereoelectronic substituent effects in saturated main group molecules: Severe problems of current Kohn-Sham density functional theory [J].

Grimme, S. ;

Steinmetz, M. ;

Korth, M. .

JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 2007, 3 (01) :42-45

[8] Seemingly simple stereoelectronic effects in alkane isomers and the implications for Kohn-Sham density functional theory [J].

Grimme, Stefan .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (27) :4460-4464

[9] Reliable low-cost theoretical procedures for studying addition-fragmentation in RAFT polymerization [J].

Izgorodina, EI ;

Coote, ML .

JOURNAL OF PHYSICAL CHEMISTRY A, 2006, 110 (07) :2486-2492

[10] Trends in R-X bond dissociation energies (R = Me, Et, i-Pr, t-Bu; X = H, CH3, OCH3, OH, F):: A surprising shortcoming of density functional theory [J].

Izgorodina, EI ;

Coote, ML ;

Radom, L .

JOURNAL OF PHYSICAL CHEMISTRY A, 2005, 109 (33) :7558-7566

← 1 2 3 →