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A framework for developing new approximate electronic structure methods is presented, in which the correlation energy of a many-electron system in the ground state is computed as in the single-reference second-order many-body perturbation…

Chemical Physics · Physics 2011-06-15 Dimitri Laikov

We show that the traditional concept of the uniform electron gas (UEG) --- a homogeneous system of finite density, consisting of an infinite number of electrons in an infinite volume --- is inadequate to model the UEGs that arise in finite…

Chemical Physics · Physics 2012-02-07 Peter M. W. Gill , Pierre-François Loos

With the eigenfunctional theory, we study a general interacting electron system, and give a rigorous expression of its ground state energy which is composed of two parts, one part is contributed by the non-interacting electrons, and another…

Materials Science · Physics 2007-12-07 Yu-Liang Liu

The principles of density-functional theory are studied for finite lattice systems represented by graphs. Surprisingly, the fundamental Hohenberg-Kohn theorem is found void in general, while many insights into the topological structure of…

Quantum Physics · Physics 2022-01-13 Markus Penz , Robert van Leeuwen

A critical challenge for density functional theory (DFT) in practice is its limited ability to treat static electron correlation, leading to errors in its prediction of charges, multiradicals, and reaction barriers. Recently, we combined…

Chemical Physics · Physics 2024-11-05 Daniel Gibney , Jan-Niklas Boyn , David A. Mazziotti

Delivering the full benefits of first principles calculations to battery materials demands the development of accurate and computationally-efficient electronic structure methods that incorporate the effects of the electrolyte environment…

Mobile charge in an electrolytic solution can in principle be represented as the divergence of ionic polarization. After adding explicit solvent polarization a finite volume of electrolyte can then be treated as a composite non-uniform…

Soft Condensed Matter · Physics 2021-03-03 Michiel Sprik

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

Linear scaling density functional theory approaches to electronic structure are often based on the tendency of electrons to localize even in large atomic and molecular systems. However, in many cases of actual interest, for example in…

Chemical Physics · Physics 2022-03-25 Marcel David Fabian , Ben Shpiro , Roi Baer

The Hohenberg-Kohn theorem of density functional theory (DFT) for the case of electrons interacting with an external magnetic field (that couples to spin only) is examined in more detail than previously. A unexpected generalization is…

Strongly Correlated Electrons · Physics 2009-10-31 H. Eschrig , W. E. Pickett

Recent work shows that density functional theory calculations accurately describe materials exhibiting turbostratic disorder between layers of incommensurate constituents. These calculations approximate one of the constituents as a finite…

Materials Science · Physics 2016-11-23 Sven P. Rudin

The uniform electron gas (UEG), a hypothetical system with finite homogenous electron density composed by an infinite number of electrons in a box of infinite volume, is the practical pillar of density-functional theory (DFT) and the…

Chemical Physics · Physics 2022-04-05 Pierre-François Loos , Michael Seidl

Based on the Schrodinger equation, exact expressions for the non-relativistic particle energy in the local external field and the external field potential are derived as inhomogeneous density functionals. On this basis, it is shown that,…

Statistical Mechanics · Physics 2011-03-24 V. B. Bobrov , S. A. Trigger

Density Functional Theory (DFT) is one of the most widely used methods for "ab initio" calculations of the structure of atoms, molecules, crystals, surfaces, and their interactions. Unfortunately, the customary introduction to DFT is often…

Physics Education · Physics 2010-12-07 Nathan Argaman , Guy Makov

A major challenge in modelling interfacial processes in electrochemical (EC) devices is performing simulations at constant potential. This requires an open-boundary description of the electrons, so that they can enter and leave the…

Chemical Physics · Physics 2023-11-07 Margherita Buraschi , Andrew P. Horsfield , Clotilde S. Cucinotta

The ground state energy of a system of electrons and nuclei is proven to be a variational functional of the conditional electronic density $n_R(\mathbf{r})$, the nuclear wavefunction $\chi(R)$ and an induced vector potential $A_{\mu}(R)$…

Chemical Physics · Physics 2016-11-08 Ryan Requist , E. K. U. Gross

We present an accurate free-energy functional for liquid water written in terms of a set of effective potential fields in which fictitious noninteracting water molecules move. The functional contains an \emph{exact} expression of the…

Soft Condensed Matter · Physics 2011-04-19 Johannes Lischner , T. A. Arias

A solid ionic conductor with cation conductivity in the interelectrode region is studied. Due to their large size, the anions are considered fixed and form a homogeneous neutralizing electric background. The model can be used to describe…

Statistical Mechanics · Physics 2022-07-04 I. Kravtsiv , G. Bokun , M. Holovko , N. Prokopchuk , D. di Caprio

The non-relativistic interacting electron gas in an external field of positively charged massive cores is dealt with in the scheme of second quantization. Ladder operators that change between stationary states of contiguous energy…

Quantum Physics · Physics 2025-02-27 Miguel Lagos

An analysis shows that the ground state of the inhomogeneous system of interacting electrons in the static external field, which satisfies the thermodynamic limit, can be consistently described only using the Green function theory based on…

Statistical Mechanics · Physics 2014-09-02 V. B. Bobrov