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We present the WCCR10 data set of ten ligand dissociation energies of large cationic transition metal complexes for the assessment of approximate exchange--correlation functionals. We analyze nine popular functionals, namely BP86, BP86-D3,…

Chemical Physics · Physics 2014-09-30 Thomas Weymuth , Erik P. A. Couzijn , Peter Chen , Markus Reiher

We have revisited the MOBH35 (Metal-Organic Barrier Heights, 35 reactions) benchmark [Iron, M. A.; Janes, T. J. Phys. Chem. A 2019, 123 (17), 3761-3781; ibid. 2019, 123, 6379-6380] for realistic organometallic catalytic reactions, using…

Chemical Physics · Physics 2022-02-09 Emmanouil Semidalas , Jan M. L. Martin

Density functional theory (DFT) embedding provides a formally exact framework for interfacing correlated wave-function theory (WFT) methods with lower-level descriptions of electronic structure. Here, we report techniques to improve the…

Chemical Physics · Physics 2015-06-12 Jason D. Goodpaster , Taylor A. Barnes , Frederick R. Manby , Thomas F. Miller

We estimate the prediction sensitivity with respect to Hartree-Fock exchange in approximate density functionals for representative Fe(II) and Fe(III) octahedral complexes. Based on the observation that the range of parameters spanned by the…

Materials Science · Physics 2015-07-16 Efthymios I. Ioannidis , Heather J. Kulik

Accurate computational predictions of band gaps are of practical importance to the modeling and development of semiconductor technologies, such as (opto)electronic devices and photoelectrochemical cells. Among available electronic-structure…

Materials Science · Physics 2021-03-16 Nicole E. Kirchner-Hall , Wayne Zhao , Yihuang Xiong , Iurii Timrov , Ismaila Dabo

By incorporating the improved empirical atom-atom dispersion corrections from DFT-D3 [Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. J. Chem. Phys. 2010, 132, 154104], two long-range corrected (LC) hybrid density functionals are proposed.…

Chemical Physics · Physics 2013-01-15 You-Sheng Lin , Guan-De Li , Shan-Ping Mao , Jeng-Da Chai

The availability of accurate computational tools for modeling and simulation is vital to accelerate the discovery of materials capable of storing hydrogen (H2) under given parameters of pressure swing and temperature. Previously, we…

Chemical Physics · Physics 2021-02-08 Srimukh Prasad Veccham , Martin Head-Gordon

Density functionals with a range-separated treatment of the exchange energy are known to improve upon their semilocal forerunners and fixed-fraction hybrids. The conversion of a given semilocal functional into its short-range analog is not…

Chemical Physics · Physics 2019-09-09 Dimitri N. Laikov

While in principle exact, Kohn-Sham density functional theory -- the workhorse of computational chemistry -- must rely on approximations for the exchange-correlation functional. Despite staggering successes, present-day approximations still…

Density Functional Theory (DFT) calculations are being routinely used to identify new material candidates that approach activity near fundamental limits imposed by thermodynamics or scaling relations. DFT calculations have finite…

Materials Science · Physics 2018-04-10 Dilip Krishnamurthy , Vaidish Sumaria , Venkatasubramanian Viswanathan

Improving the predictive capability of molecular properties in ab initio simulations is essential for advanced material discovery. Despite recent progress making use of machine learning, utilizing deep neural networks to improve quantum…

Chemical Physics · Physics 2021-09-22 Muhammad F. Kasim , Sam M. Vinko

We investigate the impact of choosing regressors and molecular representations for the construction of fast machine learning (ML) models of thirteen electronic ground-state properties of organic molecules. The performance of each…

We propose a multiconfigurational hybrid density-functional theory which rigorously combines a multiconfiguration self-consistent-field calculation with a density-functional approximation based on a linear decomposition of the…

Chemical Physics · Physics 2012-08-20 Kamal Sharkas , Andreas Savin , Hans Jørgen Aa. Jensen , Julien Toulouse

The band-gap problem and other systematic failures of approximate functionals are explained from an analysis of total energy for fractional charges. The deviation from the correct intrinsic linear behavior in finite systems leads to…

Materials Science · Physics 2009-11-13 Paula Mori-Sánchez , Aron J. Cohen , Weitao Yang

Machine learning has emerged as a powerful tool for predicting molecular properties in chemical reaction networks with reduced computational cost. However, accurately predicting energies of transition state (TS) structures remains a…

Chemical Physics · Physics 2025-04-29 Stefan Gugler , Markus Reiher

We present a purely numerical approach in Cartesian grid, for efficient computation of Hartree-Fock (HF) exchange contribution in the HF and density functional theory models. This takes inspiration from a recently developed algorithm [Liu…

Chemical Physics · Physics 2019-04-05 Abhisek Ghosal , Tanmay Mandal , Amlan K. Roy

Density functional theory (DFT) is the most promising method for calculating quantum properties of molecules and materials at moderate and large scales. However, commonly used density functional approximations (DFAs) have systematic…

Chemical Physics · Physics 2026-03-24 Yichen Fan , Jacob Z. Williams , Weitao Yang

Density functional theory (DFT) in chemistry and materials science aims for "chemical accuracy," but this goal is challenged by the need to approximate the exact exchange-correlation (XC) energy functional. The r$^2$SCAN, meta-generalized…

Density-functional theory simplifies many-electron calculations by approximating the exchange and correlation interactions with a one-electron operator that is a functional of the density. Hybrid functionals incorporate some amount of exact…

Materials Science · Physics 2021-02-03 John Vinson

In this article, we investigate the role of the self-interaction error in the simulation of collisions using time-dependent density functional theory (TDDFT) and Ehrenfest dynamics. We compare many different approximations of the exchange…

Chemical Physics · Physics 2017-05-03 Edwin E. Quashie , Bidhan C. Saha , Xavier Andrade , Alfredo A. Correa
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