Discontinuities of the exchange-correlation kernel and charge-transfer excitations in time-dependent density-functional theory

被引：75

作者：

Hellgren, Maria ^{[1
]}

Gross, E. K. U. ^{[1
]}

机构：

[1] Max Planck Inst Microstruct Phys, D-06120 Halle, Germany

来源：

PHYSICAL REVIEW A | 2012年 / 85卷 / 02期

关键词：

EXCITED-STATES; ENERGIES; FREQUENCY;

D O I：

10.1103/PhysRevA.85.022514

中图分类号：

O43 [光学];

学科分类号：

070207 ; 0803 ;

摘要：

We identify the key property that the exchange-correlation (XC) kernel of time-dependent density-functional theory must have in order to describe long-range charge-transfer excitations. We show that the discontinuity of the XC potential as a function of particle number induces a space-and frequency-dependent discontinuity of the XC kernel that diverges as r -> 8. In a combined donor-acceptor system, the same discontinuity compensates for the vanishing overlap between the acceptor and donor orbitals, thereby yielding a finite correction to the Kohn-Sham eigenvalue differences. This mechanism is illustrated to first order in the Coulomb interaction.

引用

页数：6

共 39 条

[1] EXACT RESULTS FOR THE CHARGE AND SPIN-DENSITIES, EXCHANGE-CORRELATION POTENTIALS, AND DENSITY-FUNCTIONAL EIGENVALUES [J].

ALMBLADH, CO ;

VONBARTH, U .

PHYSICAL REVIEW B, 1985, 31 (06) :3231-3244

[2]

[Anonymous], 2000, Strong Coulomb Correlation in Electronic Structure: Beyond the Local Density Approximation

[3] Excitations in time-dependent density-functional theory [J].

Appel, H ;

Gross, EKU ;

Burke, K .

PHYSICAL REVIEW LETTERS, 2003, 90 (04) :4

[4] PRODUCT-BASIS METHOD FOR CALCULATING DIELECTRIC MATRICES [J].

ARYASETIAWAN, F ;

GUNNARSSON, O .

PHYSICAL REVIEW B, 1994, 49 (23) :16214-16222

[5]

Casida M. E., 1996, THEORET COMPUT CHEM

[6] Long-range charge-transfer excited states in time-dependent density functional theory require non-local exchange [J].

Dreuw, A ;

Weisman, JL ;

Head-Gordon, M .

JOURNAL OF CHEMICAL PHYSICS, 2003, 119 (06) :2943-2946

[7] Charge transfer in time-dependent density-functional theory via spin-symmetry breaking [J].

Fuks, Johanna I. ;

Rubio, Angel ;

Maitra, Neepa T. .

PHYSICAL REVIEW A, 2011, 83 (04)

[8] Nonuniqueness of magnetic fields and energy derivatives in spin-polarized density functional theory [J].

Gal, T. ;

Ayers, P. W. ;

De Proft, F. ;

Geerlings, P. .

JOURNAL OF CHEMICAL PHYSICS, 2009, 131 (15)

[9] Exchange and correlation kernels at the resonance frequency: Implications for excitation energies in density-functional theory [J].

Gonze, X ;

Scheffler, M .

PHYSICAL REVIEW LETTERS, 1999, 82 (22) :4416-4419

[10] CORRELATION-ENERGY FUNCTIONAL AND ITS HIGH-DENSITY LIMIT OBTAINED FROM A COUPLING-CONSTANT PERTURBATION EXPANSION [J].

GORLING, A ;

LEVY, M .

PHYSICAL REVIEW B, 1993, 47 (20) :13105-13113

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