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Empirical fitting of parameters in approximate density functionals is common. Such fits conflate errors in the self-consistent density with errors in the energy functional, but density-corrected DFT (DC-DFT) separates these two. We…

Chemical Physics · Physics 2020-12-02 Suhwan Song , Stefan Vuckovic , Eunji Sim , Kieron Burke

Although many programs have been published for fully numerical Hartree--Fock (HF) or density functional (DF) calculations on atoms, we are not aware of any that support hybrid DFs, which are popular within the quantum chemistry community…

Chemical Physics · Physics 2019-08-19 Susi Lehtola

The stretching of closed-shell molecules is a qualitative problem for restricted Hartree-Fock that is usually circumvented by the use of unrestricted Hartree-Fock (UHF). UHF is well known to break the spin symmetry at the Coulson-Fischer…

Chemical Physics · Physics 2015-06-23 Paula Mori-Sánchez , Aron J. Cohen

In this work we consider a numerically solvable model of a two-electron diatomic molecule to study a recently proposed approximation based on the density-functional theory of so-called strictly correlated electrons (SCE). We map out the…

Strongly Correlated Electrons · Physics 2019-02-13 Luis Cort , Soeren Ersbak Bang Nielsen , Robert van Leeuwen

We derive a local approximation for the correlation energy in two-dimensional electronic systems. In the derivation we follow the scheme originally developed by Colle and Salvetti for three dimensions, and consider a Gaussian approximation…

Strongly Correlated Electrons · Physics 2008-11-21 S. Pittalis , E. Rasanen , M. Marques

Within density-functional theory, the local-density approximation (LDA) correlation functional is typically built by fitting the difference between the near-exact and Hartree-Fock (HF) energies of the uniform electron gas (UEG), together…

Chemical Physics · Physics 2017-05-01 Fergus J. M. Rogers , Caleb J. Ball , Pierre-François Loos

The treatment of atomic anions with Kohn-Sham density functional theory (DFT) has long been controversial since the highest occupied molecular orbital (HOMO) energy, $E_{HOMO}$, is often calculated to be positive with most approximate…

Chemical Physics · Physics 2019-03-20 Lindsey N. Anderson , M. Belén Oviedo , Bryan M. Wong

Most approximate exchange-correlation functionals used within density functional theory are constructed as the sum of two distinct contributions for exchange and correlation. Separating the exchange component from the entire functional is…

Condensed Matter · Physics 2009-10-28 Claudia Filippi , C. J. Umrigar , Xavier Gonze

The construction of density-functional approximations is explored by modeling the adiabatic connection em locally, using energy densities defined in terms of the electrostatic potential of the exchange-correlation hole. These local models…

Chemical Physics · Physics 2016-05-04 Stefan Vuckovic , Tom Irons , Andreas Savin , Andrew M. Teale , Paola Gori-Giorgi

We derive and implement symmetry-projected Hartree-Fock-Bogoliubov (HFB) equations and apply them to the molecular electronic structure problem. All symmetries (particle number, spin, spatial, and complex conjugation) are deliberately…

Strongly Correlated Electrons · Physics 2012-02-15 Gustavo E. Scuseria , Carlos A. Jimenez-Hoyos , Thomas M. Henderson , Kousik Samanta , Jason K. Ellis

In both molecular physics and condensed matter theory, deeper understanding of the correlation energy density epsilon_c (r) remains a high priority. By adopting Loewdin's definition of correlation energy as the difference between the exact…

Other Condensed Matter · Physics 2008-04-04 N. H. March , A. Cabo , F. Claro , G. G. N. Angilella

A simple comparison between the exact and approximate correlation components U of the electron-electron repulsion energy of several states of few-electron harmonium atoms with varying confinement strengths provides a superior validation…

Chemical Physics · Physics 2017-11-16 Jerzy Cioslowski , Mario Piris , Eduard Matito

We have performed self-consistent calculations for first and second row atoms using a variant of density-functional theory, the optimized effective potential method, with an approximation due to Krieger, Li and Iafrate and a…

chem-ph · Physics 2009-10-28 Tobias Grabo , E. K. U. Gross

A method for constructing semianalytical strongly correlated wave functions for single and molecular quantum dots is presented. It employs a two-step approach of symmetry breaking at the Hartree-Fock level and of subsequent restoration of…

Mesoscale and Nanoscale Physics · Physics 2009-11-07 Constantine Yannouleas , Uzi Landman

The evaluation of exact (Hartree--Fock, HF) exchange operator is a crucial ingredient for the accurate description of electronic structure in periodic systems through ab initio and hybrid density functional approaches. An efficient…

Chemical Physics · Physics 2020-10-28 Xiao Wang , Cannada A. Lewis , Edward F. Valeev

Self-consistent-field (SCF) approximations formulated using Hartree-Fock (HF) or Kohn-Sham Density Functional Theory (KS-DFT) both have the potential to yield multiple solutions. However, the formal relationship between multiple solutions…

Chemical Physics · Physics 2021-01-06 Rhiannon A. Zarotiadis , Hugh G. A. Burton , Alex J. W. Thom

Model Hamiltonians with long-range interaction yield energies that are corrected taking into account the universal behavior of the electron-electron interaction at short range. Although the intention of the paper is to explore the…

Chemical Physics · Physics 2020-10-28 Andreas Savin

Many-electron systems at substantial finite temperatures and densities present a major challenge to density functional theory. Very little is known about the free-energy behavior over the temperature range of interest, for example, in the…

Materials Science · Physics 2012-01-25 Travis Sjostrom , Frank E. Harris , S. B. Trickey

We introduce a novel energy functional for ground-state electronic-structure calculations. Its fundamental variables are the natural spin-orbitals of the implied singlet many-body wave function and their joint occupation probabilities. The…

Chemical Physics · Physics 2015-06-23 Ralph Gebauer , Morrel H. Cohen , Roberto Car

We combine density-functional theory with density-matrix functional theory to get the best of both worlds. This is achieved by range separation of the electronic interaction which permits to rigorously combine a short-range density…

Chemical Physics · Physics 2015-05-19 Daniel R. Rohr , Julien Toulouse , Katarzyna Pernal