Insights from Coulomb and exchange intracules

被引：27

作者：

Gill, PMW ^{[1
]}

Lee, AM ^{[1
]}

Nair, N ^{[1
]}

Adamson, RD ^{[1
]}

机构：

[1] Univ Cambridge, Dept Chem, Cambridge CB2 1EW, England

来源：

JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM | 2000年 / 506卷

关键词：

density functional theory; J- and K-intracules; Coulomb energy; exchange energy;

D O I：

10.1016/S0166-1280(00)00423-1

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：

We contend that the dependence of traditional density functional theory (DFT) on the one-electron density alone is both its strength and its weakness. We argue that progress beyond Kohn-Sham DFT involves the introduction of two-electron information and present intracules as a natural and concise source of this. We define special cases called the J- and K-intracules and discuss these in the context of both model systems and real molecules. (C) 2000 Elsevier Science B.V. All rights reserved.

引用

收藏

页码：303 / 312

页数：10

相关论文

共 34 条

[1] EFFECTS OF ELECTRON CORRELATION IN X-RAY + ELECTRON DIFFRACTION [J].

BARTELL, LS ;

GAVIN, RM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1964, 86 (17) :3493-&

[2] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].

BECKE, AD .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652

[3] DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].

BECKE, AD .

PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100

[4] CORRELATION AND X-RAY SCATTERING .2. ATOMIC BERYLLIUM [J].

BENESCH, R ;

SMITH, VH .

ACTA CRYSTALLOGRAPHICA SECTION A-CRYSTAL PHYSICS DIFFRACTION THEORETICAL AND GENERAL CRYSTALLOGRAPHY, 1970, A 26 (NOV1) :586-&

[5] INTRACULE DENSITIES AND ELECTRON CORRELATION IN THE HYDROGEN MOLECULE [J].

BOYD, RJ ;

SARASOLA, C ;

UGALDE, JM .

JOURNAL OF PHYSICS B-ATOMIC MOLECULAR AND OPTICAL PHYSICS, 1988, 21 (14) :2555-2561

[6] COULOMB HOLE IN SOME EXCITED-STATES OF HELIUM [J].

BOYD, RJ ;

COULSON, CA .

JOURNAL OF PHYSICS B-ATOMIC MOLECULAR AND OPTICAL PHYSICS, 1973, 6 (05) :782-793

[7] ANGULAR ASPECTS OF ELECTRON CORRELATION AND THE COULOMB HOLE [J].

BOYD, RJ ;

YEE, MC .

JOURNAL OF CHEMICAL PHYSICS, 1982, 77 (07) :3578-3582

[8] Fast evaluation of electron intracule and extracule densities on large grids of points [J].

Cioslowski, J ;

Liu, GH .

JOURNAL OF CHEMICAL PHYSICS, 1996, 105 (10) :4151-4158

[9] Electron intracule densities and Coulomb holes from energy-derivative two-electron reduced density matrices [J].

Cioslowski, J ;

Liu, GH .

JOURNAL OF CHEMICAL PHYSICS, 1998, 109 (19) :8225-8231

[10] ELECTRON INTRACULE DENSITIES WITH CORRECT ELECTRON COALESCENCE CUSPS FROM HILLER-SUCHER-FEINBERG-TYPE IDENTITIES [J].

CIOSLOWSKI, J ;

STEFANOV, BB ;

TAN, A ;

UMRIGAR, CJ .

JOURNAL OF CHEMICAL PHYSICS, 1995, 103 (14) :6093-6103

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