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Empirical fitting of parameters in approximate density functionals is common. Such fits conflate errors in the self-consistent density with errors in the energy functional, but density-corrected DFT (DC-DFT) separates these two. We…

Chemical Physics · Physics 2020-12-02 Suhwan Song , Stefan Vuckovic , Eunji Sim , Kieron Burke

Diffuse atomic orbital basis sets have proven to be essential to obtain accurate interaction energies, especially in regard to non-covalent interactions. However, they also have a detrimental impact on the sparsity of the one-particle…

Chemical Physics · Physics 2025-05-27 Henryk Laqua , Linus Bjarne Dittmer , Martin Head-Gordon

Multi-configurational wave functions are known to describe electronic structure across a Born-Oppenheimer surface qualitatively correct. However, for quantitative reaction energies, dynamical correlation originating from the many…

Chemical Physics · Physics 2020-04-16 Christopher J. Stein , Markus Reiher

Density functional theory (DFT), one of the most widely utilized methods available to computational chemistry, fails to describe systems with statically correlated electrons. To address this shortcoming, in previous work we transformed DFT…

Chemical Physics · Physics 2023-01-02 Daniel Gibney , Jan-Niklas Boyn , David A. Mazziotti

We recently introduced an efficient methodology to perform density-corrected Hartree-Fock density functional theory (DC(HF)-DFT) calculations and an extension to it we called "corrected" HF DFT (C(HF)-DFT). In this work, we take a further…

Chemical Physics · Physics 2023-11-10 Daniel Graf , Alex J. W. Thom

In a previous contribution (Mol. Phys. {\bf 103}, xxxx, 2005), we established the suitability of density functional theory (DFT) for the calculation of molecular anharmonic force fields. In the present work, we have assessed a wide variety…

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

For the theoretical understanding of the reactivity of complex chemical systems accurate relative energies between intermediates and transition states are required. Despite its popularity, density functional theory (DFT) often fails to…

Chemical Physics · Physics 2016-06-23 Gregor N. Simm , Markus Reiher

Density functional theory (DFT) is an exact alternative formulation of quantum mechanics, in which it is possible to calculate the total energy, the spin and the charge density of many-electron systems in the ground state. In practice, it…

Atomic Physics · Physics 2014-03-25 Uri Argaman , Guy Makov , Eli Kraisler

We propose a new molecular simulation framework that combines the transferability, robustness and chemical flexibility of an ab initio method with the accuracy and efficiency of a machine learned force field. The key to achieve this mix is…

Computational Physics · Physics 2020-01-08 Sebastian Dick , Marivi Fernandez-Serra

We present an accurate local density-functional for electronic-structure calculations within the density functional theory (DFT). The functional is derived by analyzing the structure of the standard perturbative expansion of the correlation…

Materials Science · Physics 2024-11-28 Mario Benites , Angel Rosado , Efstratios Manousakis

From the perspective of perturbation theory, we propose a systematic procedure for the evaluation of the derivative discontinuity (DD) of the exchange-correlation energy functional in Kohn-Sham density functional theory (KS-DFT), wherein…

Chemical Physics · Physics 2013-01-17 Jeng-Da Chai , Po-Ta Chen

When developing and assessing density functional theory methods, a finite basis set is usually employed. In most cases, however, the issue of basis set dependency is neglected. Here, we assess several basis sets and functionals. In…

Chemical Physics · Physics 2007-05-23 A. Daniel Boese , Jan M. L. Martin , Nicholas C. Handy

Predicting interfacial thermodynamics across molecular and continuum scales remains a central challenge in computational science. Classical density functional theory (cDFT) provides a first-principles route to connect microscopic…

Computational Physics · Physics 2026-01-01 Edoardo Monti , Peter Yatsyshin , Konstantinos Gkagkas , Andrew B. Duncan

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

The rapidly growing interest in simulating condensed-phase materials using quantum chemistry methods calls for a library of high-quality Gaussian basis sets suitable for periodic calculations. Unfortunately, most standard Gaussian basis…

Chemical Physics · Physics 2022-06-07 Hong-Zhou Ye , Timothy C. Berkelbach

The stochastic density functional theory (DFT) [Phys. Rev. Lett. 111, 106402 (2013)] is a valuable linear scaling approach to Kohn-Sham DFT that does not rely on the sparsity of the density matrix. Linear (and often sub-linear) scaling is…

Chemical Physics · Physics 2019-02-20 Ming Chen , Roi Baer , Daniel Neuhauser , Eran Rabani

Using multiwavelets, we have obtained total energies and corresponding atomization energies for the GGA-PBE and hybrid-PBE0 density functionals for a test set of 211 molecules with an unprecedented and guaranteed $\mu$Hartree accuracy.…

The thermodynamic approach to density functional theory (DFT) is used to derive a versatile theoretical framework for the treatment of finite-temperature (and in the limit, zero temperature) Bose-Einstein condensates (BECs). The simplest…

Quantum Gases · Physics 2015-05-20 Nathan Argaman , Y. B. Band

We analyze the methodology and the performance of subsystem density functional theory (DFT) with meta-generalized gradient approximation (meta-GGA) exchange-correlation functionals for non-bonded systems. Meta-GGA functionals depend on the…

Other Condensed Matter · Physics 2015-05-05 S. Śmiga , E. Fabiano , S. Laricchia , L. A. Constantin , F. Della Sala

Density functional simulations of condensed phase water are typically inaccurate, due to the inaccuracies of approximate functionals. A recent breakthrough showed that the SCAN approximation can yield chemical accuracy for pure water in all…

Chemical Physics · Physics 2023-02-10 Suhwan Song , Stefan Vuckovic , Youngsam Kim , Hayoung Yu , Eunji Sim , Kieron Burke