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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…

Mesoscale and Nanoscale Physics · Physics 2015-05-30 M. Hellgren , E. K. U. Gross

The fundamental gap is a central quantity in the electronic structure of matter. Unfortunately, the fundamental gap is not generally equal to the Kohn-Sham gap of density functional theory (DFT), even in principle. The two gaps differ…

Materials Science · Physics 2015-09-01 Eli Kraisler , Leeor Kronik

We propose a new approach to approximate the exchange and correlation (XC) functional in density functional theory. The XC potential is considered as an electrostatic potential, generated by a fictitious XC density, which is in turn a…

Chemical Physics · Physics 2013-05-29 Xavier Andrade , Alán Aspuru-Guzik

The derivative discontinuity of the exchange-correlation functional of density-functional theory is cast as the difference of two types of electron affinities. We show that standard Kohn-Sham calculations can be used to calculate both…

Chemical Physics · Physics 2007-12-13 F. P. Rosselli , A. B. F. da Silva , K. Capelle

We provide a new derivation of a formula for the Fukui function of density-functional chemical reactivity theory which incorporates the discontinuities in the Kohn-Sham reference system. Orbital relaxations are described in terms of the…

Chemical Physics · Physics 2015-06-04 M. Hellgren , E. K. U. Gross

Electronic structures are fully determined by the exchange-correlation (XC) potential. In this work, we develop a new method to construct reliable XC potentials by properly mixing the exact exchange and the local density approximation…

Chemical Physics · Physics 2024-08-06 Chen Huang

The electronic exchange-correlation (XC) kernel constitutes a fundamental input for the estimation of a gamut of material properties such as the dielectric characteristics, the thermal and electrical conductivity, or the response to an…

Computational Physics · Physics 2024-02-26 Zhandos A. Moldabekov , Maximilian Böhme , Jan Vorberger , David Blaschke , Tobias Dornheim

The reliability of density-functional calculations hinges on accurately approximating the unknown exchange-correlation (xc) potential. Common (semi-)local xc approximations lack the jump experienced by the exact xc potential as the number…

Atomic Physics · Physics 2021-01-15 M. J. P. Hodgson , E. Kraisler , E. K. U. Gross

Using an end-to-end differentiable implementation of the Kohn-Sham self-consistent field equations, we obtain an accurate neural network-based exchange and correlation (XC) functional of the electronic density. The functional is optimized…

Chemical Physics · Physics 2021-06-09 Sebastian Dick , Marivi Fernandez-Serra

The polarization-dependence of the exchange-correlation (XC) energy functional of periodic insulators within Kohn-Sham (KS) density-functional theory requires a ${\cal O} (1/q^2)$ divergence in the XC kernel for small vectors q. This…

Materials Science · Physics 2009-10-30 Ph. Ghosez , X. Gonze , R. W. Godby

We develop a scheme for building the scalar exchange-correlation (xc) kernel of time-dependent density functional theory (TDDFT) from the tensorial kernel of time-dependent {\em current} density functional theory (TDCDFT) and the Kohn-Sham…

Materials Science · Physics 2009-11-13 V. U. Nazarov , J. M. Pitarke , Y. Takada , G. Vignale , Y. -C. Chang

Perdew et al. [Phys. Rev. Lett 49, 1691 (1982)] discovered and proved two different properties of exact Kohn-Sham density functional theory (DFT): (i) The exact total energy versus particle number is a series of linear segments between…

Other Condensed Matter · Physics 2015-03-13 Tamar Stein , Jochen Autschbach , Niranjan Govind , Leeor Kronik , Roi Baer

We generalize the exact strong-interaction limit of the exchange-correlation energy of Kohn-Sham density functional theory to open systems with fluctuating particle numbers. When used in the self-consistent Kohn-Sham procedure on…

Strongly Correlated Electrons · Physics 2015-06-16 André Mirtschink , Michael Seidl , Paola Gori-Giorgi

The exact exchange-correlation (XC) potential in time-dependent density-functional theory (TDDFT) is known to develop steps and discontinuities upon change of the particle number in spatially confined regions or isolated subsystems. We…

Mesoscale and Nanoscale Physics · Physics 2019-03-27 Daniel Vieira , K. Capelle , C. A. Ullrich

We present a detailed study of the exact-exchange (EXX) kernel of time-dependent density functional theory with an emphasis on its discontinuity at integer particle numbers. It was recently found that this exact property leads to sharp…

Chemical Physics · Physics 2015-06-17 M. Hellgren , E. K. U. Gross

Capturing the discontinuous shift by $\Delta$ in the exact exchange-correlation (xc) potential is the standard proposal for calculating the fundamental gap, $E_\mathrm{g}$, from the Kohn-Sham (KS) gap, $\varepsilon_\mathrm{g}$, within KS…

Materials Science · Physics 2021-01-14 M. J. P. Hodgson , J. Wetherell , Emmanuel Fromager

A diagrammatic expansion for the dynamic exchange-correlation kernel f_xc of time dependent density functional theory is formulated. It is shown that f_xc has no singularities at Kohn-Sham transition energies in every order of the…

Condensed Matter · Physics 2009-11-07 I. V. Tokatly , R. Stubner , O. Pankratov

Solving the fundamental and optical gap problems, which yield information about charged and neutral excitations in electronic systems, is one of the biggest challenge in density-functional theory (DFT). Despite their intrinsic difference,…

Chemical Physics · Physics 2018-08-29 Bruno Senjean , Emmanuel Fromager

We present an exact expression for the frequency-dependent Kohn-Sham exact-exchange (EXX) kernel for periodic insulators, which can be employed for the calculation of electronic response properties within time-dependent (TD)…

Materials Science · Physics 2016-08-31 Yong-Hoon Kim , Andreas Goerling

We investigate fundamental properties of meta-generalized-gradient approximations (meta-GGAs) to the exchange-correlation energy functional, which have an implicit density dependence via the Kohn-Sham kinetic-energy density. To this…

Chemical Physics · Physics 2014-12-10 F. G. Eich , Maria Hellgren
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