相关论文: The derivative discontinuity of the exchange-corre…

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…

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…

Discontinuous changes in the electronic structure upon infinitesimal changes to the Hamiltonian are demonstrated. Remarkably, these are revealed in one and two electron molecular systems if the realm of the nuclear charge is extended to be…

Standard approximations for the exchange-correlation functional are known to deviate from linear dependence of the energy on the electron and spin numbers (in -space). Violation of this flat-plane condition underlies the failure of all…

The derivative discontinuity in the exact exchange-correlation potential of ensemble Density Functional Theory (DFT) is investigated at the specific integer number that corresponds to the maximum number of bound electrons, $J_{max}$. A…

Standard approximations for the exchange-correlation functional have been found to give big errors for the linearity condition of fractional charges, leading to delocalization error, and the constancy condition of fractional spins, leading…

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…

Many references exist in the density functional theory (DFT) literature to the chemical potential of the electrons in an atom or a molecule. The origin of this notion has been the identification of the Lagrange multiplier $\mu = \partial…

Density functional approximations to the exchange-correlation energy of Kohn-Sham theory, such as the local density approximation and generalized gradient approximations, lack the well-known integer discontinuity, a feature that is critical…

The discontinuous character of the exact exchange-correlation $(xc)$ energy functional of Density Functional Theory is shown to arise naturally in the subband spectra of semiconductor quantum wells. Using an \emph{ab-initio} $xc$…

We derive an exact representation of the exchange-correlation energy within density functional theory (DFT) which spawns a class of approximations leading to correct long-range asymptotic behavior. In what amounts to be the simplest…

We show that the energy functional of ensemble Density Functional Theory (DFT) [Perdew et al., Phys. Rev. Lett. 49, 1691 (1982)] in systems with attractive interactions is a convex function of the fractional particle number N and is given…

Charge transfer plays a crucial role in many processes of interest in physics, chemistry, and bio-chemistry. In many applications the size of the systems involved calls for time-dependent density functional theory (TDDFT) to be used in…

This work merges two different types of many-electron ensembles, namely the Theophilou-Gross-Oliveira-Kohn ensembles of ground and neutrally-excited states, and the more recent $N$-centered ensembles of neutral and charged ground states. On…

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…

Density Functional Theory (DFT) is one of the most widely used methods for "ab initio" calculations of the structure of atoms, molecules, crystals, surfaces, and their interactions. Unfortunately, the customary introduction to DFT is often…

Two (so-called left and right) variants of N-centered ensemble density-functional theory (DFT) [Senjean and Fromager, Phys. Rev. A 98, 022513 (2018)] are presented. Unlike the original formulation of the theory, these variants allow for the…

It has long been postulated that within density-functional theory (DFT) the total energy of a finite electronic system is convex with respect to electron count, so that 2 E_v[N_0] <= E_v[N_0 - 1] + E_v[N_0 + 1]. Using the…

In the exact Kohn-Sham density-functional theory (DFT), the total energy versus the number of electrons is a series of linear segments between integer points. However, commonly used approximate density functionals produce total energies…

Exchange interactions are a manifestation of the quantum mechanical nature of the electrons and play a key role in predicting the properties of materials from first principles. In density functional theory (DFT), a widely used approximation…