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The scaling of neutral atoms to large $Z$, combining periodicity with a gradual trend to homogeneity, is a fundamental probe of density functional theory, one that has driven recent advances in understanding both the kinetic and…

Chemical Physics · Physics 2018-01-08 Antonio C. Cancio , Jeremy J. Redd

We perform systematic density functional theory (DFT) calculations to assess the performance of various exchange-correlation potentials $V_{xc}$ in describing the chalcogenide GaM$_4$Q$_8$ lacunar spinels (M=Mo, V, Nb, Ta; Q=S, Se). We…

Materials Science · Physics 2019-09-25 Yiqun Wang , Danilo Puggioni , James M. Rondinelli

Molecular-orbital-based machine learning (MOB-ML) enables the prediction of accurate correlation energies at the cost of obtaining molecular orbitals. Here, we present the derivation, implementation, and numerical demonstration of MOB-ML…

Chemical Physics · Physics 2021-04-07 Sebastian J. R. Lee , Tamara Husch , Feizhi Ding , Thomas F. Miller

An accurate analytical parametrization for the exchange-correlation free energy of the homogeneous electron gas, including interpolation for partial spin-polarization, is derived via thermodynamic analysis of recent restricted path integral…

Chemical Physics · Physics 2015-06-17 Valentin V. Karasiev , Travis Sjostrom , James Dufty , S. B. Trickey

The Jacob's ladder of density functional theory (DFT) proposes the compelling view that by extending the form of successful approximations -- being guided by exact conditions and selected (least empirical) norms -- upper rungs will do…

Materials Science · Physics 2025-02-25 Jacques K. Desmarais , Alessandro Erba , Giovanni Vignale , Stefano Pittalis

We extend the previously proposed one-parameter double-hybrid density-functional theory [K. Sharkas, J. Toulouse, and A. Savin, J. Chem. Phys. 134, 064113 (2011)] to meta-generalized-gradient-approximation (meta-GGA) exchange-correlation…

Chemical Physics · Physics 2014-02-27 Sidi Ould Souvi , Kamal Sharkas , Julien Toulouse

The homogeneous electron gas (HEG) is a key ingredient in the construction of most exchange-correlation functionals of density-functional theory. Often, the energy of the HEG is parameterized as a function of its spin density $n$, leading…

Chemical Physics · Physics 2021-02-10 Susi Lehtola , Miguel A. L. Marques

Originating from a broken spatial inversion symmetry, ferroelectricity is a functionality of materials with an electric dipole that can be switched by external electric fields. Spontaneous polarization is a crucial ferroelectric property,…

Materials Science · Physics 2017-08-03 Yubo Zhang , Jianwei Sun , John P. Perdew , Xifan Wu

The flexibility of common generalized gradient approximation for the exchange-correlation energy is investigated by monitoring the equilibrium volume of transition metals. It is shown that no universal gradient-level approximation yielding…

Materials Science · Physics 2015-06-05 H. Levämäki , L. Vitos , M. P. J. Punkkinen , K. Kokko

We present a study of the equilibrium properties of $sp$-bonded solids within the pseudopotential approach, employing recently proposed generalized gradient approximation (GGA) exchange correlation functionals. We analyze the effects of the…

Condensed Matter · Physics 2016-08-31 Yumin Juan , Efthimios Kaxiras

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 performed density functional calculations to estimate the formation energies of intermetallic alloys. We used two semilocal approximations, the generalized gradient approximation (GGA) by Perdew-Burke-Ernzerhof (PBE) and the strongly…

Materials Science · Physics 2020-11-25 Niraj K. Nepal , Santosh Adhikari , Bimal Neupane , Adrienn Ruzsinszky

During the past decades, approximate Kohn-Sham density-functional theory schemes garnered many successes in computational chemistry and physics; yet the performance in the prediction of spin state energetics is often unsatisfactory. By…

Other Condensed Matter · Physics 2023-05-05 Joao Paulo Almeida de Mendonca , Lorenzo A. Mariano , Emilie Devijver , Noel Jakse , Roberta Poloni

We derive analytic energy gradients of the driven similarity renormalization group (DSRG) multireference second-order perturbation theory (MRPT2) using the method of Lagrange multipliers. In the Lagrangian, we impose constraints for a…

Chemical Physics · Physics 2021-09-30 Shuhe Wang , Chenyang Li , Francesco A. Evangelista

An alternative type of approximation for the exchange and correlation functional in density functional theory is proposed. This approximation depends on a variable $u$ that is able to detect inhomogeneities in the electron density $\rho$…

Materials Science · Physics 2019-01-02 Fabien Tran , Peter Blaha

We model the exchange-correlation (XC) energy density of the Si crystal and atom as calculated by variational Monte Carlo (VMC) methods with a gradient analysis beyond the local density approximation (LDA). We find the Laplacian of the…

Materials Science · Physics 2009-11-11 Antonio C. Cancio , M. Y. Chou

We discuss the crystal, electronic, and magnetic structures of $\mathrm{La_{2-x}Sr_{x}CuO_{4}}$ (LSCO) for $x=0.0$ and $x=0.25$ employing 13 density functional approximations, representing the local, semi-local, and hybrid…

In modeling low-dimensional electronic nanostructures, the evaluation of the electron-electron interaction is a challenging task. Here we present an accurate and practical density-functional approach to the two-dimensional many-electron…

Strongly Correlated Electrons · Physics 2010-10-29 S. Pittalis , E. Rasanen

Analytical forces have been derived in the Lagrangian framework for several random phase approximation (RPA) correlated total energy methods based on the range separated hybrid (RSH) approach, which combines a short-range density functional…

Chemical Physics · Physics 2016-03-16 Bastien Mussard , Peter G. Szalay , János G. Ángyán

Density functional theory (DFT) in chemistry and materials science aims for "chemical accuracy," but this goal is challenged by the need to approximate the exact exchange-correlation (XC) energy functional. The r$^2$SCAN, meta-generalized…