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Large atomic-orbital (AO) basis sets of at least triple and preferably quadruple-zeta (QZ) size are required to adequately converge Kohn-Sham density functional theory (DFT) calculations towards the complete basis set limit. However,…

Chemical Physics · Physics 2025-12-02 Anthony O. Lara , Justin J. Talbot , Zhe Wang , Martin Head-Gordon

Static correlation is a difficult problem for density-functional theory (DFT) as it arises in cases of degenerate or quasi-degenerate states where a multideterminantal wave function provides the simplest reasonable first approximation to…

Chemical Physics · Physics 2024-01-01 Abraham Ponra , Carolyne Bakasa , Anne Justine Etindele , Mark E. Casida

Density functional theory (DFT) based modeling of electronic excited states is of importance for investigation of the photophysical/photochemical properties and spectroscopic characterization of large systems. The widely used linear…

Chemical Physics · Physics 2021-05-11 Diptarka Hait , Martin Head-Gordon

Traditional finite-temperature Kohn-Sham density functional theory (KSDFT) has an unfavorable scaling with respect to the electron number or at high temperatures. The evaluation of the ground-state density in KSDFT can be replaced by the…

Computational Physics · Physics 2022-10-05 Qianrui Liu , Mohan Chen

While quantum computers have shown significant promise for electronic structure calculations, their potential to accelerate density functional theory (DFT) calculations remains unclear. In this work, we present a qubit-efficient encoding…

We study the accuracy of Kohn-Sham density functional theory (DFT) for warm- and hot-dense matter (WDM and HDM). Specifically, considering a wide range of systems, we perform accurate ab initio molecular dynamics simulations with…

Computational Physics · Physics 2024-11-21 Phanish Suryanarayana , Arpit Bhardwaj , Xin Jing , Shashikant Kumar , John E. Pask

We present a reformulation of QM/MM as a fully quantum mechanical theory of interacting subsystems, all treated at the level of density functional theory (DFT). For the MM subsystem, which lacks orbitals, we assign an ad hoc electron…

Ranking the binding of small molecules to protein receptors through physics-based computation remains challenging. Though inroads have been made using free energy methods, these fail when the underlying classical mechanical force fields are…

Chemical Physics · Physics 2020-04-21 Narbe Mardirossian , Yuhang Wang , David A. Pearlman , Garnet Kin-Lic Chan , Toru Shiozaki

Quantum-chemical processes in liquid environments impact broad areas of science, from molecular biology to geology to electrochemistry. While density-functional theory (DFT) has enabled efficient quantum-mechanical calculations which…

Chemical Physics · Physics 2017-10-16 Kendra Letchworth-Weaver , Ravishankar Sundararaman , T. A. Arias

Variational optimization of orbitals in time-independent density functional calculations of excited electronic states presents a significant challenge, as excited states typically correspond to saddle points on the electronic energy…

Chemical Physics · Physics 2026-04-02 Yorick L. A. Schmerwitz , Elli Selenius , Gianluca Levi

The reconstruction of the exchange-correlation potential from accurate ab initio electron densities can provide insights into the limitations of the currently available approximate functionals and provide guidance for devising improved…

Strongly Correlated Electrons · Physics 2013-02-05 Katharina Boguslawski , Christoph R. Jacob , Markus Reiher

Adopting an accurate kinetic energy density functional (KEDF) to characterize the noninteracting kinetic energy within the framework of orbital-free density functional theory (OFDFT) is challenging. We propose a new form of the non-local…

Computational Physics · Physics 2024-11-15 Liang Sun , Yuanbo Li , Mohan Chen

Combining classical density functional theory (cDFT) with quantum mechanics (QM) methods offers a computationally efficient alternative to traditional QM/molecular mechanics (MM) approaches for modeling mixed quantum-classical systems at…

Statistical Mechanics · Physics 2026-02-17 Guillaume Jeanmairet , Maxime Labat , Emmanuel Giner

Variational excited-state density functional theory (DFT) enables the calculation of excited states at a cost comparable to ground-state calculations, but single-configuration approaches often suffer from spin contamination. We implement…

Chemical Physics · Physics 2026-05-28 Michael J. Sahre , Marco Romanelli , Martijn Marsman , Leticia González , Georg Kresse

Accurate description of deformed atomic nuclei by the orbital-free density functional theory has been a longstanding textbook challenge, due to the difficulty in accounting for the intricate quantum shell effects that are present in such…

Nuclear Theory · Physics 2024-12-31 X. H. Wu , Z. X. Ren , P. W. Zhao

Here we present a density matrix based KS inversion method formulated entirely within a Gaussian basis representation to optimize a KS potential matrix that reproduces a target electron density. Inverse Kohn-Sham (KS) density functional…

Chemical Physics · Physics 2026-03-24 Ziwei Chai , Sandra Luber

This chapter presents controlled approximations of Kohn-Sham density functional theory (DFT) that enable very large scale simulations. The work is motivated by the study of defects in crystalline solids, though the ideas can be used in…

Materials Science · Physics 2021-12-14 Kaushik Bhattacharya , Vikram Gavini , Michael Ortiz , Mauricio Ponga , Phanish Suryanarayana

Quantum mechanical calculations of core electron binding energies (CEBEs) leading to 2p hole states are relevant to interpreting L-edge x-ray photo-electron spectroscopy (XPS), as well as higher edges. Orbital-optimized density functional…

Chemical Physics · Physics 2025-07-31 Richard Kang , Leonardo A. Cunha , Diptarka Hait , Martin Head-Gordon

Electronic structure calculation of atoms and molecules, in the past few decades has largely been dominated by density functional methods. This is primarily due to the fact that this can account for electron correlation effects in a…

Chemical Physics · Physics 2013-07-12 Amlan K. Roy

We introduce a machine learning (ML) supervised model function that is inspired by the variational principle of physics. This ML hypothesis evolutionary method, termed ML-Omega, allows us to go from data to differential equation(s)…

Chemical Physics · Physics 2024-05-29 Juan I. Rodriguez , Ulises A. Vergara-Beltran