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We derive an exact representation of the exchange-correlation energy within density functional theory (DFT) which spawns a class of approximations leading to correct long-range asymptotic behavior. In what amounts to be the simplest…

Materials Science · Physics 2009-11-10 Roi Baer , Daniel Neuhauser

Hydrogen bonding is an important non-covalent interaction that plays a major role in molecular self-organization and supramolecular structures. It can be described accurately with ab initio quantum chemical wave function methods, which…

Chemical Physics · Physics 2025-05-16 Usman Ahmed , Mikael P. Johansson , Susi Lehtola , Dage Sundholm

The recent progress on global optimizations of covariant energy density functionals (CEDFs) and global calculations of binding energies within the covariant density functional theory (CDFT) has been analyzed and reviewed. Recently developed…

Nuclear Theory · Physics 2025-11-04 A. V. Afanasjev , B. Osei , A. Dalbah

Due to efficient scaling with electron number N, density functional theory (DFT) is widely used for studies of large molecules and solids. Restriction of an exact mean-field theory to local potential functions has recently been questioned.…

Other Condensed Matter · Physics 2015-06-24 Robert K. Nesbet

The ground states of the actinides and their compounds continue to be matters of considerable controversies. Experimentally, Americium-I (Am-I) is a non-magnetic dhcp metal whereas theoretically an anti-ferromagnetic ground state is…

Strongly Correlated Electrons · Physics 2015-05-14 Raymond Atta-Fynn , Asok K. Ray

Calculating highly accurate thermochemical properties of condensed matter via wave function-based approaches (such as e.g. Hartree-Fock or hybrid functionals) has recently attracted much interest. We here present two strategies providing…

This chapter concerns with the recent development of a new DFT methodology for accurate, reliable prediction of many-electron systems. Background, need for such a scheme, major difficulties encountered, as well as their potential remedies…

Chemical Physics · Physics 2019-04-19 Amlan K. Roy

Density functional theory (DFT) is used to rationalize magnetic parameters of hydrated electron trapped in alkaline glasses as observed using Electron Paramagnetic Resonance (EPR) and Electron Spin Echo Envelope Modulation (ESEEM)…

General Physics · Physics 2016-09-28 I. A. Shkrob

This review presents a concise, yet comprehensive discussion on the evolution of theoretical methods employed to determine the ground and excited states of molecules in weak and strong magnetic fields. The weak-field cases have been studied…

Atomic and Molecular Clusters · Physics 2021-05-31 Mihir Date , R. W. A Havenith

We show that the Hartree-Fock (HF) results cannot be reproduced within the framework of Kohn-Sham (KS) theory because the single-particle densities of finite systems obtained within the HF calculations are not $v$-representable, i.e., do…

Other Condensed Matter · Physics 2009-11-10 M. Ya. Amusia , A. Z. Msezane , V. R. Shaginyan , D. Sokolovski

A uniform derivation is presented of the self-consistent field equations in a finite basis set. Both restricted and unrestricted Hartree-Fock (HF) theory as well as various density functional (DF) approximations are considered. The unitary…

Computational Physics · Physics 2020-03-10 Susi Lehtola , Frank Blockhuys , Christian Van Alsenoy

The ground-state Hartree-Fock (HF) wavefunction of the Hooke's atom is not known in closed form, contrary to the exact solution. The single HF orbital involved has thus far been studied using expansion techniques only, leading to slightly…

Atomic Physics · Physics 2008-05-05 Ragot Sebastien

The density functional scheme for calculating the pair density is presented by means of the constrained-search technique. The resultant single-particle equation takes the form of the modified Hartree-Fock equation which contains the kinetic…

Strongly Correlated Electrons · Physics 2015-06-25 Masahiko Higuchi , Katsuhiko Higuchi

Density functional theory has been an essential analysis tool for both theoretical and experimental chemists since accurate hybrid functionals were developed. Here we propose a local hybrid method derived from the optimized effective…

Chemical Physics · Physics 2017-03-24 Jaewook Kim , Kwangwoo Hong , Sang-Yeon Hwang , Seongok Ryu , Sunghwan Choi , Woo Youn Kim

The evaluation of exact (Hartree--Fock, HF) exchange operator is a crucial ingredient for the accurate description of electronic structure in periodic systems through ab initio and hybrid density functional approaches. An efficient…

Chemical Physics · Physics 2020-10-28 Xiao Wang , Cannada A. Lewis , Edward F. Valeev

Electrons in zero external magnetic field can be studied with density functional theory (DFT) or with spin-DFT (SDFT). The latter is normally used for open shell systems because its approximations appear to model better the exchange and…

Chemical Physics · Physics 2022-04-06 Timothy Callow , Benjamin Pearce , Nikitas Gidopoulos

The diffusion Monte Carlo (DMC), auxiliary field quantum Monte Carlo (AFQMC), and equation-of-motion coupled cluster (EOM-CC) methods are used to calculate the electron binding energy (EBE) of the non-valence anion state of a model…

Chemical Physics · Physics 2021-02-03 Shiv Upadhyay , Amanda Dumi , James Shee , Kenneth D. Jordan

The very good performance of modern density functional theory for molecular geometries and harmonic vibrational frequencies has been well established. We investigate the performance of density functional theory (DFT) for quartic force…

Chemical Physics · Physics 2007-05-23 A. Daniel Boese , Wim Klopper , Jan M. L. Martin

Few-electron systems confined in two-dimensional parabolic quantum dots at high magnetic fields are studied by the Hartree-Fock (HF) and exact diagonalization methods. A generalized multicenter Gaussian basis is proposed in the HF method. A…

Mesoscale and Nanoscale Physics · Physics 2009-11-10 B. Szafran , S. Bednarek , J. Adamowski , M. B. Tavernier , E. Anisimovas , F. M. Peeters

We investigate the binding of single and quadruple hydrogen molecules on a positively charged Ca ion. By comparing with benchmark quantum Monte Carlo (QMC) calculations we demonstrate wide variability in other more approximate electronic…

Materials Science · Physics 2010-08-12 Michal Bajdich , Fernando A. Reboredo , P. R. C. Kent