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Under a certain scaling, the electron densities of finite systems become both large and slowly-varying, so that the gradient expansions of the density functionals for the Kohn-Sham kinetic and exchange energies become asymptotically exact…

Quantum Physics · Physics 2009-11-13 John P. Perdew , Lucian A. Constantin , Espen Sagvolden , Kieron Burke

We present a physically motivated correlation functional belonging to the meta-generalized gradient approximation (meta-GGA) rung, which can be supplemented with long-range dispersion corrections without introducing double-counting of…

Using the methodology of conditional-probability density functional theory, and several mild assumptions, we calculate the temperature-dependence of the Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA). This…

Chemical Physics · Physics 2023-08-17 John Kozlowski , Dennis Perchak , Kieron Burke

By using the quantum Ising chain as a test bed and treating the spin polarization along the external transverse field as the "generalized density", we examine the performance of different levels of density functional approximations parallel…

Computational Physics · Physics 2021-10-27 Jiahao Mao , Haifeng Tang , Wenhui Duan , Zheng Liu

Exact exchange contributions are known to crucially affect electronic states, which in turn govern covalent bond formation and breaking in chemical species. Empirically averaging the exact exchange admixture over compositional degrees of…

We derive the next order correction to the Dirac exchange energy for the free electron gas in a box with zero boundary conditions in the thermodynamic limit. The correction is of the order of the surface area of the box, and comes from…

Chemical Physics · Physics 2025-03-24 Thiago Carvalho Corso , Gero Friesecke

Lieb and Oxford (1981) derived rigorous lower bounds, in the form of local functionals of the electron density, on the indirect part of the Coulomb repulsion energy. The greatest lower bound for a given electron number N depends…

Applied Physics · Physics 2022-06-22 John P. Perdew , Jianwei Sun

We report the successful adaptation of the quasi-boson approximation, a technique traditionally employed in nuclear physics, to the analysis of the two-dimensional electron gas. We show that the correlation energy estimated from this…

Strongly Correlated Electrons · Physics 2025-05-05 Tobias M. R. Wolf , Chunli Huang

We calculate the electronic structure of several atoms and small molecules by direct minimization of the Self-Interaction Corrected Local Density Approximation (SIC-LDA) functional. To do this we first derive an expression for the gradient…

Condensed Matter · Physics 2009-10-28 S. Goedecker , C. J. Umrigar

Recent high resolution Compton scattering experiments clearly reveal that there are fundamental limitations to the conventional local density approximation (LDA) based description of the ground state electron momentum density (EMD) in…

Strongly Correlated Electrons · Physics 2007-10-11 B. Barbiellini , A. Bansil

The exchange-correlation hole and potential of the homogeneous electron gas have been investigated within the random-phase approximation, employing the plasmon-pole approximation for the linear density response function. The angular…

Strongly Correlated Electrons · Physics 2023-04-12 K. Karlsson , F. Aryasetiawan

A new functional form for the exchange enhancement in the generalized gradient approximation within density functional theory is given. The functional form satisfies the constraints used to construct the Perdew-Burke-Ernzerhof (PBE)…

Materials Science · Physics 2009-11-11 Georg K. H. Madsen

Successful modern generalized gradient approximations (GGA) are biased toward atomic energies. Restoration of the first-principles gradient expansion for the exchange energy over a wide range of density gradients eliminates this bias. We…

The "ACFD-RPA" correlation energy functional has been widely applied to a variety of systems to successfully predict energy differences, and less successfully predict absolute correlation energies. Here we present a parameter-free…

Atomic Physics · Physics 2015-06-11 Tim Gould

One of the standard generalized-gradient approximations (GGAs) in use in modern electronic-structure theory, PBE, and a recently proposed modification designed specifically for solids, PBEsol, are identified as particular members of a…

Materials Science · Physics 2015-05-13 Luana S. Pedroza , Antonio J. R. da Silva , Klaus Capelle

The circular $\beta$ ensemble for $\beta =1,2$ and 4 corresponds to circular orthogonal, unitary and symplectic ensemble respectively as introduced by Dyson. The statistical state of the eigenvalues is then a determinantal point process…

Mathematical Physics · Physics 2025-09-08 Peter J. Forrester , Bo-Jian Shen

In recent work, generalized gradient approximations (GGA's) have been constructed from the energy density of the Airy gas for exchange but not for correlation. We report the random phase approximation (RPA) conventional correlation energy…

Materials Science · Physics 2009-06-30 Lucian A. Constantin , Adrienn Ruzsinszky , John P. Perdew

The random phase approximation (RPA) has emerged as a prominent first-principles method in material science, particularly to study the adsorption and chemisorption of small molecules on surfaces. However, its widespread application is…

Materials Science · Physics 2025-09-01 Edoardo Spadetto , Pier Herman Theodoor Philipsen , Arno Förster , Lucas Visscher

We discuss, simplify, and improve the spin-dependent correction of L.A. Constantin et al., Phys. Rev. B 84, 233103, for atomization energies, and develop a density parameter of the form $v\propto |\nabla n|/n^{10/9}$, found from the…

Chemical Physics · Physics 2013-02-01 L. A. Constantin , E. Fabiano , F. Della Sala

The non-relativistic large-$Z$ expansion of the exchange energy of neutral atoms provides an important input to modern non-empirical density functional approximations. Recent works report results of fitting the terms beyond the dominant…

Chemical Physics · Physics 2023-10-09 Jeremy J. Redd , Antonio C. Cancio , Nathan Argaman , Kieron Burke