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Slater determinants have underpinned quantum chemistry for nearly a century, yet their full potential has remained challenging to exploit. In this work, we show that a variational wavefunction composed of a few hundred optimized…

Chemical Physics · Physics 2026-04-17 Clemens Giuliani , Jannes Nys , Rocco Martinazzo , Giuseppe Carleo , Riccardo Rossi

Kohn-Sham density functional theory calculations using conventional diagonalization based methods become increasingly expensive as temperature increases due to the need to compute increasing numbers of partially occupied states. We present…

Chemical Physics · Physics 2022-03-23 Qimen Xu , Xin Jing , Boqin Zhang , John E. Pask , Phanish Suryanarayana

The route to reliable quantum nanoelectronic devices hinges on precise control of the electrostatic environment. For this reason, accurate methods for electrostatic simulations are essential in the design process. The most widespread…

Mesoscale and Nanoscale Physics · Physics 2023-02-28 Waldemar Svejstrup , Andrea Maiani , Kevin Van Hoogdalem , Karsten Flensberg

We introduce a machine learning method in which energy solutions from the Schrodinger equation are predicted using symmetry adapted atomic orbitals features and a graph neural-network architecture. \textsc{OrbNet} is shown to outperform…

We present a density difference based analysis for a range of orbital--dependent Kohn--Sham functionals. Results for atoms, some members of the neon isoelectronic series and small molecules are reported and compared with ab initio…

Chemical Physics · Physics 2015-01-22 I. Grabowski , A. M. Teale , E. Fabiano , S. Smiga , A. Buksztel , F. Della Sala

A new class of orbital-dependent exchange-correlation (xc) potentials for applications in noncollinear spin-density-functional theory is developed. Starting from the optimized effective potential (OEP) formalism for the exact exchange…

Mesoscale and Nanoscale Physics · Physics 2018-08-01 Carsten A. Ullrich

Density-potential functional theory (DPFT) is an alternative formulation of orbital-free density functional theory that may be suitable for modeling the electronic structure of large systems. To date, DPFT has been applied mainly to quantum…

Materials Science · Physics 2023-04-21 Martin-Isbjörn Trappe , William C. Witt , Sergei Manzhos

Orbital-free (OF) methods promise significant speed-up of computations based on density functional theory (DFT). In this field, the development of accurate kinetic-energy density functionals remains an open question. In this chapter we…

Materials Science · Physics 2013-05-03 Constantine Yannouleas , Uzi Landman

Developing a reliable kinetic energy density functional within orbital-free density functional theory remains a long-standing challenge, particularly for atomic and molecular systems. A major difficulty lies in the absence of a systematic…

Chemical Physics · Physics 2025-10-22 Priya Priya , Anuvab Panda , Saswata Basu , Mainak Sadhukhan

An accurate non-gradient-expansion based correction to Thomas--Fermi is developed using solvable model. The used model is a system of $N$ non-interacting electrons moving independently in the Coulomb field of the nuclear charge. The…

Quantum Physics · Physics 2015-06-04 Alexey Sergeev , Raka Jovanovic , Sabre Kais , Fahhad H Alharbi

Solving the Euler equation which corresponds to the energy minimum of a density functional expressed in orbital-free form involves related but distinct computational challenges. One is the choice between all-electron and pseudo-potential…

Materials Science · Physics 2015-05-30 V. V. Karasiev , S. B. Trickey

We present a non-decomposable approximation for the non-additive non-interacting kinetic energy (NAKE) for covalent bonds based on the exact behavior of the von Weizs\"{a}cker (vW) functional in regions dominated by one orbital. This…

Chemical Physics · Physics 2018-11-14 Kaili Jiang , Jonathan Nafziger , Adam Wasserman

We introduce a new approach to density functional theory based on kinetic theory, showing that the Kohn-Sham equations can be derived as a macroscopic limit of a suitable Boltzmann kinetic equation in the limit of small mean free path…

Chemical Physics · Physics 2015-06-15 M. Mendoza , S. Succi , H. J. Herrmann

The auxiliary functions provide efficient computation of integrals arising at the self-consistent field (SCF) level for molecules using Slater-type bases. This applies both in relativistic and non-relativistic electronic structure theory.…

Chemical Physics · Physics 2017-11-29 A. Bagci , P. E. Hoggan

We introduce an energy functional for ground-state electronic structure calculations. Its variables are the natural spin-orbitals of singlet many-body wave functions and their joint occupation probabilities deriving from controlled…

Chemical Physics · Physics 2016-12-04 Ralph Gebauer , Morrel H. Cohen , Roberto Car

Nonlocal kinetic energy density functionals (KEDFs) with density-dependent kernels are currently the most accurate functionals available for orbital-free density functional theory (OF-DFT) calculations. However, despite advances in…

Materials Science · Physics 2024-12-05 Yongshuo Chen , Cheng Ma , Boning Cui , Tian Cui , Wenhui Mi , Qiang Xu , Yanchao Wang , Yanming Ma

Recently, we introduced (e-print arXiv:1407.7128) {\em local reduced density matrix functional theory} (local RDMFT), a theoretical scheme capable of incorporating static correlation effects in Kohn-Sham equations. Here, we apply local…

Chemical Physics · Physics 2014-11-07 Nektarios N. Lathiotakis , Nicole Helbig , Angel Rubio , Nikitas I. Gidopoulos

In orbital-free density functional theory the kinetic potential (KP), the functional derivative of the kinetic energy density functional, appears in the Euler equation for the electron density and may be more amenable to simple…

Other Condensed Matter · Physics 2015-05-13 Jeng-Da Chai , Vincent L. Ligneres , Gregory Ho , Emily A. Carter , John D. Weeks

The original formulation (Phys. Rev. Lett. 119, 063002, 2017) of the natural orbital functional - second-order M{\o}ller-Plesset (NOF-MP2) method is based on the MP2 that uses the canonical Hartree-Fock molecular orbitals. The current work…

Chemical Physics · Physics 2018-08-22 Mario Piris

This paper derives and demonstrates a new, purely density-based ab initio approach for calculation of the energies and properties of many-electron systems. It is based upon the discovery of relationships that govern the "mechanics" of the…

Chemical Physics · Physics 2024-09-04 James C. Ellenbogen