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A double-atom partitioning of the molecular one-electron density matrix is used to describe atoms and bonds. All calculations are performed in Hilbert space. The concept of atomic weight functions (familiar from Hirshfeld analysis of the…

It seems self-evident that a density functional calculation should be normalized to the number of electrons in the system. We present multiple examples where the accuracy of the approximate energy is improved (sometimes greatly) by…

Chemical Physics · Physics 2026-03-13 Adam Clay , Kiril Datchev , Wenlan Miao , Adam Wasserman , Kimberly J. Daas , Kieron Burke

The superposition of atomic potentials (SAP) approach has recently been shown to be a simple and efficient way to initialize electronic structure calculations [S. Lehtola, J. Chem. Theory Comput. 15, 1593 (2019)]. Here, we study the…

Computational Physics · Physics 2020-04-13 Susi Lehtola , Lucas Visscher , Eberhard Engel

We present model-assisted density fitting (MADF) basis set generator, an algorithm for generating primitive atomic Gaussian density fitting (DF) basis sets (DFBSs) from a contracted Gaussian orbital basis set (OBS). The MADF algorithm…

Chemical Physics · Physics 2025-10-14 Kshitijkumar A. Surjuse , Edward F. Valeev

The Coulomb exchange and correlation energy density functionals for electron systems are applied to nuclear systems. It is found that the exchange functionals in the generalized gradient approximation provide agreements with the exact-Fock…

Nuclear Theory · Physics 2019-12-09 Tomoya Naito , Ryosuke Akashi , Gianluca Colò , Haozhao Liang , Xavier Roca-Maza

Reporting extensions of a recently developed approach to density functional theory with correct long-range be-havior (Phys. Rev. Lett. 94, 043002 (2005)). The central quantities are a splitting functional gamma[n] and a complementary…

Materials Science · Physics 2017-09-13 Ester Livshits , Roi Baer

We introduce a new basis function (the spherical gaussian) for electronic structure calculations on spheres of any dimension $D$. We find \alert{general} expressions for the one- and two-electron integrals and propose an efficient…

Chemical Physics · Physics 2015-06-09 Peter M. W. Gill , Pierre-François Loos , Davids Agboola

We present an efficient algorithm for one- and two-component relativistic exact-decoupling calculations. Spin-orbit coupling is thus taken into account for the evaluation of relativistically transformed (one-electron) Hamiltonian. As the…

Chemical Physics · Physics 2013-05-10 Daoling Peng , Nils Middendorf , Florian Weigend , Markus Reiher

Using the optimized effective potential method in conjunction with the semi-analytical approximation due to Krieger, Li and Iafrate, we have performed fully self-consistent exact exchange-only density-functional calculations for diatomic…

chem-ph · Physics 2008-02-03 T. Grabo , E. K. U. Gross

Plane-wave electronic-structure predictions based upon orbital-dependent density-functional theory (OD-DFT) approximations, such as hybrid density-functional methods and self-interaction density-functional corrections, are severely affected…

Materials Science · Physics 2011-10-19 Yanli Li , Ismaila Dabo

Kohn-Sham density functional theory is one of the most widely used electronic structure theories. In the pseudopotential framework, uniform discretization of the Kohn-Sham Hamiltonian generally results in a large number of basis functions…

Numerical Analysis · Mathematics 2015-05-27 Lin Lin , Jianfeng Lu , Lexing Ying , E. Weinan

The leading-order dispersion and exchange-dispersion terms in symmetry-adapted perturbation theory (SAPT), $E^{(20)}_{\rm disp}$ and $E^{(20)}_{\rm exch-disp}$, suffer from slow convergence to the complete basis set limit. To alleviate this…

Chemical Physics · Physics 2021-01-26 Monika Kodrycka , Konrad Patkowski

We consider estimating the parameters of a Gaussian mixture density with a given number of components best representing a given set of weighted samples. We adopt a density interpretation of the samples by viewing them as a discrete Dirac…

Machine Learning · Statistics 2025-04-03 Daniel Frisch , Uwe D. Hanebeck

Complex Gaussian basis sets are optimized to accurately represent continuum radial wavefunctions over the whole space. First, attention is put on the technical ability of the optimization method to get more flexible series of Gaussian…

Chemical Physics · Physics 2025-11-04 Stéphanie Laure Egome Nana , Arnaud Leclerc , Lorenzo Ugo Ancarani

Most approximate exchange-correlation functionals used within density functional theory are constructed as the sum of two distinct contributions for exchange and correlation. Separating the exchange component from the entire functional is…

Condensed Matter · Physics 2009-10-28 Claudia Filippi , C. J. Umrigar , Xavier Gonze

In density functional theory, charge density is the core attribute of atomic systems from which all chemical properties can be derived. Machine learning methods are promising in significantly accelerating charge density prediction, yet…

Computational Physics · Physics 2024-05-30 Xiang Fu , Andrew Rosen , Kyle Bystrom , Rui Wang , Albert Musaelian , Boris Kozinsky , Tess Smidt , Tommi Jaakkola

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

In the recent work of S. Sharma \emph{et al.}, (arxiv.org: arxiv:0912.1118), a single-electron spectrum associated with the natural orbitals was defined as the derivative of the total energy with respect to the occupation numbers at half…

Chemical Physics · Physics 2012-03-07 E. N. Zarkadoula , S. Sharma , J. K. Dewhurst , E. K. U. Gross , N. N. Lathiotakis

Density fitting (DF), also known as the resolution of the identity (RI), is a widely used technique in quantum chemical calculations with various types of atomic basis sets - Gaussian-type orbitals, Slater-type orbitals, as well as…

Chemical Physics · Physics 2021-12-22 Susi Lehtola

We investigate the use of optimized correlation consistent gaussian basis sets for the study of insulating solids with auxiliary-field quantum Monte Carlo (AFQMC). The exponents of the basis set are optimized through the minimization of the…

Chemical Physics · Physics 2021-02-03 Miguel A. Morales , Fionn D. Malone