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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

We derive an automatic procedure for generating a set of highly localized, non-orthogonal orbitals for linear scaling quantum Monte Carlo calculations. We demonstrate the advantage of these orbitals in calculations of the total energy of…

Materials Science · Physics 2007-05-23 F. A. Reboredo , A. J. Williamson

Functionals that strive to correct for such self-interaction errors, such as those obtained by imposing the Perdew-Zunger self-interaction correction or the generalized Koopmans' condition, become orbital dependent or orbital-density…

Materials Science · Physics 2011-08-30 Cheol-Hwan Park , Andrea Ferretti , Ismaila Dabo , Nicolas Poilvert , Nicola Marzari

We demonstrate how to determine numerically nearly exact orthonormal orbitals that are optimal for evaluation of the energy of arbitrary (correlated) states of atoms and molecules by minimization of the energy Lagrangian. Orbitals are…

The exchange-correlation energy in Kohn-Sham density functional theory is expressed as a functional of the electronic density and the Kohn-Sham orbitals. An alternative to Kohn-Sham theory is to express the energy as a functional of the…

Computational Physics · Physics 2009-10-31 S. Goedecker , C. Umrigar

The current work presents a natural orbital functional (NOF) for electronic systems with any spin value independent of the external potential being considered, that is, a global NOF (GNOF). It is based on a new two-index reconstruction of…

Chemical Physics · Physics 2021-12-07 Mario Piris

The standard way to calculate the Kohn-Sham orbitals utilizes an approximation of the potential. The approximation consists in a projection of the potential into a finite subspace of basis functions. The orbitals, calculated with the…

Computational Physics · Physics 2018-11-19 Rudolf Zeller

In the density functional (DF) theory of Kohn and Sham, the kinetic energy of the ground state of a system of noninteracting electrons in a general external field is calculated using a set of orbitals. Orbital free methods attempt to…

Strongly Correlated Electrons · Physics 2009-11-13 Jeng-Da Chai , John D Weeks

We present a novel route to constructing cost-efficient semi-empirical approximations for the non-additive kinetic energy in subsystem density functional theory. The developed methodology is based on the use of Slater determinants composed…

Chemical Physics · Physics 2025-01-13 Larissa Sophie Eitelhuber , Denis G. Artiukhin

All-electron calculations play an important role in density functional theory, in which improving computational efficiency is one of the most needed and challenging tasks. In the model formulations, both nonlinear eigenvalue problem and…

Computational Physics · Physics 2020-07-29 Bin Gao , Guanghui Hu , Yang Kuang , Xin Liu

We consider a modification of the OMM energy functional which contains an $\ell^1$ penalty term in order to find a sparse representation of the low-lying eigenspace of self-adjoint operators. We analyze the local minima of the modified…

Numerical Analysis · Mathematics 2017-03-08 Jianfeng Lu , Kyle Thicke

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

The choice of molecular orbitals is decisive in configuration interaction calculations. In this letter, a democratic description of the ground and excited states follows an orthogonally constrained orbitals optimization to produce…

Quantum Physics · Physics 2023-02-16 Saad Yalouz , Vincent Robert

Variational quantum eigensolver ans\"atze hold considerable promise for ground-state energy calculations on near-term quantum hardware, yet most promising ansatz designs currently strongly depend on how well the molecular orbital basis…

The implementation of the orbital minimization method (OMM) for solving the self-consistent Kohn-Sham (KS) problem for electronic structure calculations in a basis of non-orthogonal numerical atomic orbitals of finite-range is reported. We…

Computational Physics · Physics 2014-02-06 Fabiano Corsetti

We present a novel energy-based localization procedure able to localize molecular orbitals into specific spatial regions. The method is applied to several cases including both conjugated and non-conjugated systems. The obtained localized…

Chemical Physics · Physics 2022-09-13 Tommaso Giovannini , Henrik Koch

We present a method to compute high-order derivatives of the total energy which can be used in the framework of density functional theory. We provide a proof of the $2n+1$ theorem for a general class of energy functionals in which the…

Condensed Matter · Physics 2007-05-23 Andrea Dal Corso , Francesco Mauri

We use the recently introduced single-particle states obtained from localized Deuteron wave-functions as a basis for nuclear many-body calculations. We show that energies can be substantially lowered if the natural orbits obtained from this…

Nuclear Theory · Physics 2018-05-23 Giovanni Puddu

Employing a local formula for the electron-electron interaction energy, we derive a self-consistent approximation for the total energy of a general $N$-electron system. Our scheme works as a local variant of the Thomas-Fermi approximation…

Chemical Physics · Physics 2013-10-31 E. Rasanen , A. Odriazola , I. Makkonen , A. Harju

The ground state of atoms from H to Ar was calculated using a self-interaction correction to local and gradient dependent density functionals. The correction can significantly improve the total energy and makes the orbital energies…

Atomic and Molecular Clusters · Physics 2013-08-29 Simon Klüpfel , Peter Klüpfel , Hannes Jonsson
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