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There are several approximations to the exchange-correlation functional in density-functional theory that accurately predict total energy-related properties of many-electron systems, such as binding energies, bond lengths, and crystal…

Chemical Physics · Physics 2015-09-30 Eli Kraisler , Tobias Schmidt , Stephan Kümmel , Leeor Kronik

The relative energies of different phases or polymorphs of molecular solids can be small, less than a kiloJoule/mol. Reliable description of such energy differences requires high quality treatment of electron correlations, typically beyond…

Chemical Physics · Physics 2024-02-19 Khanh Ngoc Pham , Marcin Modrzejewski , Jiří Klimeš

Ensemble Density Functional Theory (EDFT) is a promising extension to Density Functional Theory (DFT) for calculating excited states. While Kohn-Sham eigenvalue differences underestimate gaps, EDFT has been shown to provide more accurate…

Materials Science · Physics 2026-02-10 Gregory G. V. Kenning , Remi J. Leano , David A. Strubbe

By studying the lowest excitations of an exactly solvable one-dimensional molecular model, we show that components of Kohn-Sham ensembles can be used to describe charge transfers. Furthermore, we compute the approximate excitation energies…

Chemical Physics · Physics 2018-05-22 Tim Gould , Leeor Kronik , Stefano Pittalis

The analytic energy gradients in the atomic orbital representation have recently been published (J. Chem. Phys. 146, 014102, 2017) within the framework of the natural orbital functional theory (NOFT). We provide here an alternative…

Chemical Physics · Physics 2018-02-19 Ion Mitxelena , Mario Piris

We investigate fundamental properties of meta-generalized-gradient approximations (meta-GGAs) to the exchange-correlation energy functional, which have an implicit density dependence via the Kohn-Sham kinetic-energy density. To this…

Chemical Physics · Physics 2014-12-10 F. G. Eich , Maria Hellgren

A review of the approximations in any time-dependent density functional calculation of excitation energies is given. The single-pole approximation for the susceptibility is used to understand errors in popular approximations for the…

Materials Science · Physics 2007-05-23 Kieron Burke , Martin Petersilka , E. K. U. Gross

The uniform electron gas and the hydrogen atom play fundamental roles in condensed matter physics and quantum chemistry. The former has an infinite number of electrons uniformly distributed over the neutralizing positively-charged…

Chemical Physics · Physics 2016-06-22 Jianwei Sun , John P. Perdew , Zenghui Yang , Haowei Peng

We propose a machine learning based approach to develop the exchange-correlation potential of time dependent density functional theory (TDDFT). The neural network projection from the time-varying electron densities to the corresponding…

Computational Physics · Physics 2020-05-20 Yasumitsu Suzuki , Ryo Nagai , Jun Haruyama

Modern density functional theory (DFT) calculations employ the Kohn-Sham (KS) system of non-interacting electrons as a reference, with all complications buried in the exchange-correlation energy (Exc). The adiabatic connection formula gives…

Other Condensed Matter · Physics 2009-10-02 Zhenfei Liu , Kieron Burke

Gross-Oliveira-Kohn density functional theory (GOK-DFT) for ensembles is in principle very attractive, but has been hard to use in practice. A novel, practical model based on GOK-DFT for the calculation of electronic excitation energies is…

Chemical Physics · Physics 2015-07-28 Bruno Senjean , Stefan Knecht , Hans Jørgen Aa. Jensen , Emmanuel Fromager

Exact density functionals for the exchange and correlation energies are approximated in practical calculations for the ground-state electronic structure of a many-electron system. An important exact constraint for the construction of…

A partial-active-space (PAS) multi-state (MS) multi-reference second-order perturbation theory (MRPT2) for the electronic structure of strongly correlated systems of electrons, dubbed PASPT2, is formulated by linearizing the intermediate…

Chemical Physics · Physics 2026-05-21 Chunzhang Liu , Ning Zhang , Wenjian Liu

We investigate the time an electronic excitation travels in a supermolecular setup using a measurement process in an open quantum-system framework. The approach is based on the stochastic Schr\"odinger equation and uses a Hamiltonian from…

Materials Science · Physics 2013-12-09 Dirk Hofmann , Heiko Appel , Massimiliano Di Ventra , Stephan Kümmel

DFT calculations have become widespread in both chemistry and materials, because they usually provide useful accuracy at much lower computational cost than wavefunction-based methods. All practical DFT calculations require an approximation…

Chemical Physics · Physics 2022-03-15 Eunji Sim , Suhwan Song , Stefan Vuckovic , Kieron Burke

The electron density, its gradient, and the Kohn-Sham orbital kinetic energy density are the local ingredients of a meta-generalized gradient approximation (meta-GGA). We construct a meta-GGA density functional for the exchange-correlation…

Materials Science · Physics 2009-02-20 Jianmin Tao , John P. Perdew , Viktor N. Staroverov , Gustavo E. Scuseria

Double excitations are crucial to understanding numerous chemical, physical, and biological processes, but accurately predicting them remains a challenge. In this work, we explore the particle-particle random phase approximation (ppRPA) as…

Chemical Physics · Physics 2024-11-26 Jincheng Yu , Jiachen Li , Tianyu Zhu , Weitao Yang

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

The derivative discontinuity of the exchange-correlation functional of density-functional theory is cast as the difference of two types of electron affinities. We show that standard Kohn-Sham calculations can be used to calculate both…

Chemical Physics · Physics 2007-12-13 F. P. Rosselli , A. B. F. da Silva , K. Capelle

We present a range-separated linear-response time-dependent density-functional theory (TDDFT) which combines a density-functional approximation for the short-range response kernel and a frequency-dependent second-order Bethe-Salpeter…

Chemical Physics · Physics 2016-03-23 Elisa Rebolini , Julien Toulouse