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We introduce an orbital free electron density functional approximation based on alchemical perturbation theory. Given convergent perturbations of a suitable reference system, the accuracy of popular self-consistent Kohn-Sham density…

Chemical Physics · Physics 2020-05-27 Guido Falk von Rudorff , O. Anatole von Lilienfeld

Machine-learning of atomic-scale properties amounts to extracting correlations between structure, composition and the quantity that one wants to predict. Representing the input structure in a way that best reflects such correlations makes…

Chemical Physics · Physics 2021-02-02 Michael J. Willatt , Félix Musil , Michele Ceriotti

Various properties of the general two-center two-electron integral over the explicitly correlated exponential function are analyzed for the potential use in high precision calculations for diatomic molecules. A compact one dimensional…

Chemical Physics · Physics 2015-06-11 Krzysztof Pachucki

Closed-form expressions for all matrix elements required for variational calculation of the electronic structure of periodic solids have been derived using a basis of explicitly correlated Gaussians (ECGs). Periodic basis functions are…

Quantum Physics · Physics 2026-05-14 Kalman Varga

Electronic structure codes usually allow to calculate the work function as a part of the theoretical description of surfaces and processes such as adsorption thereon. This requires a proper calculation of the electrostatic potential in all…

Materials Science · Physics 2009-11-11 K. Doll

An alternative multipole expansion of the correlation term is derived. Modified spherical Bessel type functions which simplify as a summation of multiple orders of basic trigonometric functions are generated from this new method. We use…

Quantum Physics · Physics 2017-04-10 Eric Ouma Jobunga

The symmetry-projected Hartree--Fock ansatz for the electronic structure problem can efficiently account for static correlation in molecules, yet it is often unable to describe dynamic correlation in a balanced manner. Here, we consider a…

Strongly Correlated Electrons · Physics 2015-06-17 Carlos A. Jiménez-Hoyos , R. Rodríguez-Guzmán , Gustavo E. Scuseria

A simple comparison between the exact and approximate correlation components U of the electron-electron repulsion energy of several states of few-electron harmonium atoms with varying confinement strengths provides a superior validation…

Chemical Physics · Physics 2017-11-16 Jerzy Cioslowski , Mario Piris , Eduard Matito

Accurate modelling of electrostatic interactions and charge transfer is fundamental to computational chemistry, yet most machine learning interatomic potentials (MLIPs) rely on local atomic descriptors that cannot capture long-range…

Cryo-electron microscopy can now routinely deliver atomic resolution structures for a variety of biological systems. The relevance and value of these structures is directly related to their ability to help rationalize experimental…

We develop a technique for generating a set of optimized local basis functions to solve models in the Kohn-Sham density functional theory for both insulating and metallic systems. The optimized local basis functions are obtained by solving…

Computational Physics · Physics 2015-05-30 Lin Lin , Jianfeng Lu , Lexing Ying , E. Weinan

A representation of polymer self-consistent field theory equivalent to quantum density functional theory is given in terms of non-orthogonal basis sets. Molecular integrals and self-consistent equations for spherically symmetric systems…

Atomic Physics · Physics 2026-02-05 Phil A. LeMaitre , Russell B. Thompson

A relativistic version of the effective charge model for computation of observable characteristics of multi-electron atoms and ions is developed. A complete and orthogonal Dirac hydrogen basis set, depending on one parameter -- effective…

Atomic Physics · Physics 2020-07-10 K. Dzikowski , O. D. Skoromnik , I. D. Feranchuk , N. S. Oreshkina , C. H. Keitel

Reduced basis methods provide a powerful framework for building efficient and accurate emulators. Although widely applied in many fields to simplify complex models, reduced basis methods have only been recently introduced into nuclear…

Nuclear Theory · Physics 2022-10-12 Amy L. Anderson , Graham L. O'Donnell , J. Piekarewicz

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 computation of vibrational spectra of diatomic molecules through the exact diagonalization of algebraically determined matrixes based on powers of Morse coordinates is made substantially more efficient by choosing a properly adapted…

Chemical Physics · Physics 2016-09-28 Andrea Bordoni , Nicola Manini

The methods which are actively used for electronic structure calculations of low-lying states of heavy- and superheavy-element compounds are briefly described. The advantages and disadvantages of calculations with the Dirac-Coulomb-Breit…

Chemical Physics · Physics 2009-11-07 A. V. Titov , N. S. Mosyagin , T. A. Isaev , A. N. Petrov

Methods for electronic structure based on Gaussian and molecular orbital discretizations offer a well established, compact representation that forms much of the foundation of correlated quantum chemistry calculations on both classical and…

Evaluation of basic integrals over Gaussian functions, traditionally utilized for electronic structure computations on molecules and solids, is discussed in a pedagogical form.

Quantum Physics · Physics 2020-07-24 Justin T. Fermann , Edward F. Valeev

In this perspective, the various measures of electron correlation used in wavefunction theory, density functional theory and quantum information theory are briefly reviewed. We then focus on a more traditional metric based on dominant…

Chemical Physics · Physics 2023-04-07 Róbert Izsák , Aleksei V Ivanov , Nick S. Blunt , Nicole Holzmann , Frank Neese