Delocalization errors in density functionals and implications for main-group thermochemistry

被引：163

作者：

Johnson, Erin R. ^{[1
]}

Mori-Sanchez, Paula ^{[1
]}

Cohen, Aron J. ^{[1
]}

Yang, Weitao ^{[1
]}

机构：

[1] Duke Univ, Dept Chem, Durham, NC 27708 USA

来源：

JOURNAL OF CHEMICAL PHYSICS | 2008年 / 129卷 / 20期

基金：

加拿大自然科学与工程研究理事会; 美国国家科学基金会;

关键词：

association; density functional theory; enthalpy; reaction kinetics theory; thermochemistry;

D O I：

10.1063/1.3021474

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：

The difficulty of approximate density functionals in describing the energetics of Diels-Alder reactions and dimerization of aluminum complexes is analyzed. Both of these reaction classes involve formation of cyclic or bicyclic products, which are found to be underbound by the majority of functionals considered. We present a consistent view of these results from the perspective of delocalization error. This error causes approximate functionals to give too low energy for delocalized densities or too high energy for localized densities, as in the cyclic and bicyclic reaction products. This interpretation allows us to understand better a wide range of errors in main-group thermochemistry obtained with popular density functionals. In general, functionals with minimal delocalization error should be used for theoretical studies of reactions where there is a loss of extended conjugation or formation of highly branched, cyclic, and cagelike molecules.

引用

收藏

页数：6

相关论文

共 48 条

[21] 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

[22] How to compute isomerization energies of organic molecules with quantum chemical methods [J].

Grimme, Stefan ;

Steinmetz, Marc ;

Korth, Martin .

JOURNAL OF ORGANIC CHEMISTRY, 2007, 72 (06) :2118-2126

[23] Comparison of the accurate Kohn-Sham solution with the generalized gradient approximations (GGAs) for the SN2 reaction F-+CH3F→FCH3+F-:: A qualitative rule to predict success or failure of GGAs [J].

Gritsenko, OV ;

Ensing, B ;

Schipper, PRT ;

Baerends, EJ .

JOURNAL OF PHYSICAL CHEMISTRY A, 2000, 104 (37) :8558-8565

[24] A standard set of pericyclic reactions of hydrocarbons for the benchmarking of computational methods: The performance of ab initio, density functional, CASSCF, CASPT2, and CBS-QB3 methods for the prediction of activation barriers, reaction energetics, and transition state geometries [J].

Guner, V ;

Khuong, KS ;

Leach, AG ;

Lee, PS ;

Bartberger, MD ;

Houk, KN .

JOURNAL OF PHYSICAL CHEMISTRY A, 2003, 107 (51) :11445-11459

[25] A quantum chemical study of the atomic layer deposition of Al2O3 using AlCl3 and H2O as precursors [J].

Heyman, A ;

Musgrave, CB .

JOURNAL OF PHYSICAL CHEMISTRY B, 2004, 108 (18) :5718-5725

[26] Structure and binding energies in van der Waals dimers: Comparison between density functional theory and correlated ab initio methods [J].

Johnson, ER ;

DiLabio, GA .

CHEMICAL PHYSICS LETTERS, 2006, 419 (4-6) :333-339

[27] Density functional theory based model calculations for accurate bond dissociation enthalpies. 3. A single approach for X-H, X-X, and X-Y (X, Y=C, N, O, S, halogen) bonds [J].

Johnson, ER ;

Clarkin, OJ ;

DiLabio, GA .

JOURNAL OF PHYSICAL CHEMISTRY A, 2003, 107 (46) :9953-9963

[28] A unified density-functional treatment of dynamical, nondynamical, and dispersion correlations. II. Thermochemical and kinetic benchmarks [J].

Johnson, Erin R. ;

Becke, Axel D. .

JOURNAL OF CHEMICAL PHYSICS, 2008, 128 (12)

[29] DEVELOPMENT OF THE COLLE-SALVETTI CORRELATION-ENERGY FORMULA INTO A FUNCTIONAL OF THE ELECTRON-DENSITY [J].

LEE, CT ;

YANG, WT ;

PARR, RG .

PHYSICAL REVIEW B, 1988, 37 (02) :785-789

[30] Self-interaction-free exchange-correlation functional for thermochemistry and kinetics [J].

Mori-Sánchez, P ;

Cohen, AJ ;

Yang, WT .

JOURNAL OF CHEMICAL PHYSICS, 2006, 124 (09)

← 1 2 3 4 5 →