Exact expressions for the Kohn-Sham exchange-correlation potential in terms of wave-function-based quantities

被引：45

作者：

Cuevas-Saavedra, Rogelio ^{[1
]}

Staroverov, Viktor N. ^{[1
]}

机构：

[1] Univ Western Ontario, Dept Chem, London, ON, Canada

来源：

MOLECULAR PHYSICS | 2016年 / 114卷 / 7-8期

基金：

加拿大自然科学与工程研究理事会;

关键词：

Density-functional theory; exchange-correlation potential; reduced density matrices; generalised Fock operator; Dyson orbitals; NATURAL SPIN-ORBITALS; DENSITY-MATRICES; ENERGIES; BEHAVIOR; SCF;

D O I：

10.1080/00268976.2015.1131861

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：

Several workers have deduced various exact expressions for the Kohn-Sham exchange-correlation potential in terms of quantities computable from the interacting and noninteracting wave functions of the system. We show that all these expressions can be obtained by one general method in which the interacting N-electron wave function is expanded in products of one- and (N - 1)-electron functions. Different expressions correspond to different choices of the latter functions. Our analysis unifies and clarifies the previously proposed exact treatments of the exchange-correlation potential, and suggests new ways of expressing this quantity. [GRAPHICS] .

引用

页码：1050 / 1058

页数：9

共 41 条

[1] The Kohn-Sham gap, the fundamental gap and the optical gap: the physical meaning of occupied and virtual Kohn-Sham orbital energies [J].

Baerends, E. J. ;

Gritsenko, O. V. ;

van Meer, R. .

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2013, 15 (39) :16408-16425

[2] A quantum chemical view of density functional theory [J].

Baerends, EJ ;

Gritsenko, OV .

JOURNAL OF PHYSICAL CHEMISTRY A, 1997, 101 (30) :5383-5403

[3] Ab initio density functional theory:: The best of both worlds? -: art. no. 062205 [J].

Bartlett, RJ ;

Lotrich, VF ;

Schweigert, IV .

JOURNAL OF CHEMICAL PHYSICS, 2005, 123 (06)

[4] The exchange-correlation potential in ab initio density functional theory -: art. no. 034104 [J].

Bartlett, RJ ;

Grabowski, I ;

Hirata, S ;

Ivanov, S .

JOURNAL OF CHEMICAL PHYSICS, 2005, 122 (03)

[5] Interconnection between functional derivative and effective operator approaches to ab initio density functional theory [J].

Bokhan, D ;

Schweigert, IV ;

Bartlett, RJ .

MOLECULAR PHYSICS, 2005, 103 (15-16) :2299-2307

[6] ANALYSIS OF CORRELATION IN TERMS OF EXACT LOCAL POTENTIALS - APPLICATIONS TO 2-ELECTRON SYSTEMS [J].

BUIJSE, MA ;

BAERENDS, EJ ;

SNIJDERS, JG .

PHYSICAL REVIEW A, 1989, 40 (08) :4190-4202

[7] EIGENVALUES OF DENSITY MATRICES [J].

CARLSON, BC ;

KELLER, JM .

PHYSICAL REVIEW, 1961, 121 (03) :659-&

[8] Interpretation of the Kohn-Sham orbital energies as approximate vertical ionization potentials [J].

Chong, DP ;

Gritsenko, OV ;

Baerends, EJ .

JOURNAL OF CHEMICAL PHYSICS, 2002, 116 (05) :1760-1772

[9] Kohn-Sham exchange-correlation potentials from second-order reduced density matrices [J].

Cuevas-Saavedra, Rogelio ;

Ayers, Paul W. ;

Staroverov, Viktor N. .

JOURNAL OF CHEMICAL PHYSICS, 2015, 143 (24)

[10]

DAY OW, 1974, INT J QUANTUM CHEM, P501

← 1 2 3 4 5 →