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In contrast to the original Kohn-Sham (KS) formalism, we propose a density functional theory (DFT) with fractional orbital occupations for the study of ground states of many-electron systems, wherein strong static correlation is shown to be…

Chemical Physics · Physics 2015-06-03 Jeng-Da Chai

Self-interaction is a fundamental flaw of practical Kohn-Sham Density Functional Theory (KS DFT) approximations responsible for numerous qualitative and even catastrophic shortcomings. Whereas self-interaction is easy to characterize in…

Chemical Physics · Physics 2024-07-16 Samuel A. Slattery , Edward F. Valeev

Electron density and electron momentum density, while independently tractable experimentally, bear no direct connection without going through the many-electron wave function. However, invoking a variant of the constrained-search formulation…

Atomic Physics · Physics 2009-11-11 M. K. Harbola , Rajendra R. Zope , Anjali Kshirsagar , Rajeev K. Pathak

A rigorous derivation of the density functional via the effective action in the Hohenberg-Kohn theory is outlined. Using the auxiliary field method, in which the electric coupling constant $e^2$ need not be small, we show that the loop…

Other Condensed Matter · Physics 2009-09-22 Yi-Kuo Yu

A relativistic density-functional theory based on a Fock-space effective quantum-electrodynamics (QED) Hamiltonian using the Coulomb or Coulomb-Breit two-particle interaction is developed. This effective QED theory properly includes the…

Chemical Physics · Physics 2021-05-03 Julien Toulouse

Ensemble density functional theory is a promising method for the efficient and accurate calculation of excitations of quantum systems, at least if useful functionals can be developed to broaden its domain of practical applicability. Here,…

Chemical Physics · Physics 2017-12-25 Tim Gould , Stefano Pittalis

DFT calculations have become widespread in both chemistry and materials, because they usually provide useful accuracy at much lower computational cost than wavefunction-based methods. All practical DFT calculations require an approximation…

Chemical Physics · Physics 2022-03-15 Eunji Sim , Suhwan Song , Stefan Vuckovic , Kieron Burke

A very specific ensemble of ground and excited states is shown to yield an exact formula for any excitation energy as a simple correction to the energy difference between orbitals of the Kohn-Sham ground state. This alternative scheme…

Chemical Physics · Physics 2017-07-26 Zeng-hui Yang , Aurora Pribram-Jones , Kieron Burke , Carsten A. Ullrich

We present a kinetic-energy density-functional theory and the corresponding kinetic-energy Kohn-Sham (keKS) scheme on a lattice and show that by including more observables explicitly in a density-functional approach already simple…

Chemical Physics · Physics 2018-07-23 Iris Theophilou , Florian Buchholz , F. G. Eich , Michael Ruggenthaler , Angel Rubio

We analyze the various approaches to construct exchange-correlation functionals which are able to describe states of definite spin multiplicity in the DFT realm and outline the characteristics of possible functionals consistent with the…

Chemical Physics · Physics 2019-01-04 A. L. Tchougréeff , J. G. Ángyán

We formulate the Kohn-Sham density functional theory (KS-DFT) as a statistical theory in which the electron density is deter-mined from an average of correlated stochastic densities in a trace formula. The key idea is that it is sufficient…

Materials Science · Physics 2015-06-15 Roi Baer , Daniel Neuhauser , Eran Rabani

We present a first principles strategy for developing state-specific density functional approximations for excited states. We first clarify why approaches based on conventional ground state approximations miss density-driven correlations,…

Chemical Physics · Physics 2025-06-09 Tim Gould , Stephen G Dale , Leeor Kronik , Stefano Pittalis

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…

Physics Education · Physics 2010-12-07 Nathan Argaman , Guy Makov

Recent photoabsorption measurements have revealed a rich fine structure in the collective charge-density excitation spectrum of few-electron quantum dots in the presence of magnetic fields. We have performed systematic computational studies…

Mesoscale and Nanoscale Physics · Physics 2009-10-31 C. A. Ullrich , G. Vignale

We derive the second-order approximation (PT2) to the ensemble correlation energy functional by applying the G\"{o}rling-Levy perturbation theory on the ensemble density-functional theory (EDFT). Its performance is checked by calculating…

Computational Physics · Physics 2021-11-17 Zeng-hui Yang

A rigorous derivation of the density functional in the Hohenberg-Kohn theory is presented. With no assumption regarding the magnitude of the electric coupling constant $e^2$ (or correlation), this work provides a firm basis for…

Other Condensed Matter · Physics 2010-09-20 Yi-Kuo Yu

A recent work [arXiv:2401.04685] has merged $N$-centered ensembles of neutral and charged electronic ground states with ensembles of neutral ground and excited states, thus providing a general and in-principle exact (so-called extended…

Strongly Correlated Electrons · Physics 2024-05-14 Filip Cernatic , Emmanuel Fromager

Two of the most widely used electronic structure theory methods, namely Hartree-Fock and Kohn-Sham density functional theory, both requires the iterative solution of a set of Schr\"odinger-like equations. The speed of convergence of such…

Chemical Physics · Physics 2024-06-06 S. Hazra , U. Patil , S. Sanvito

Spin is a fundamental property of any many-electron system. The ability of density functional theory to accurately predict the physical properties of a system, while varying its spin, is crucial for describing magnetic materials and…

Chemical Physics · Physics 2024-11-05 Alon Hayman , Eli Kraisler , Tamar Stein

By inverting the time-dependent Kohn-Sham equation for a numerically exact dynamics of the helium atom, we show that the dynamical step and peak features of the exact correlation potential found previously in one-dimensional models persist…

Chemical Physics · Physics 2022-07-28 Davood Dar , Lionel Lacombe , Johannes Feist , Neepa Maitra
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