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Density functional theory calculations can be used to identify dominant reaction mechanisms. However, the dominant reaction mechanism is sensitive to choice of the exchange correlation functional. Here, we demonstrate using the example case…

Materials Science · Physics 2018-09-12 Vaidish Sumaria , Dilip Krishnamurthy , Venkatasubramanian Viswanathan

The ability of several density-functional theory (DFT) exchange-correlation functionals to describe hydrogen bonds in small water clusters (dimer to pentamer) in their global minimum energy structures is evaluated with reference to second…

Materials Science · Physics 2009-07-20 Biswajit Santra , Angelos Michaelides , Matthias Scheffler

We present fully empirical exchange-correlation functionals to be used within reduced density matrix functional theory (RDMFT). These are of the popular J-K form, where the function of the occupation numbers that multiplies the Fock orbital…

Computational Physics · Physics 2017-03-03 Miguel A. L. Marques , N. N. Lathiotakis

The isostructural {\alpha}-{\gamma} phase transition in cerium is analyzed using density-functional theory with different exchange-correlation functionals, in particular the PBE0 hybrid functional and the exact- exchange plus correlation in…

Strongly Correlated Electrons · Physics 2015-06-11 Marco Casadei , Xinguo Ren , Patrick Rinke , Angel Rubio , Matthias Scheffler

Rare-earth oxides (REOs) are an important class of materials owing to their unique properties, including high ionic conductivities, large dielectric constants, and elevated melting temperatures, making them relevant to several technological…

An alternative type of approximation for the exchange and correlation functional in density functional theory is proposed. This approximation depends on a variable $u$ that is able to detect inhomogeneities in the electron density $\rho$…

Materials Science · Physics 2019-01-02 Fabien Tran , Peter Blaha

Previous work on the physical content of exchange correlation functionals that depend on both charge and spin densities is extended to elemental transition metals and a wider range of perovskite transition metal oxides. A comparison of…

Materials Science · Physics 2016-02-17 Hanghui Chen , Andrew J. Millis

Density functional theory(DFT) and Hartree-Fock(HF) calculations are reported for the family of transition metal fluorides $\mbox{ScF}_3$, $\mbox{TiF}_4$, $\mbox{VF}_5$, and $\mbox{CrF}_6$. Both HF and the local-density-aproximation (LDA)…

chem-ph · Physics 2016-08-31 Thomas V. Russo , Richard L. Martin , P. Jeffrey Hay

A new density functional theory (DFT) exchange-correlation functional for the exploration of reaction mechanisms is proposed. This new functional, denoted BMK (Boese-Martin for Kinetics), has an accuracy in the 2 kcal/mol range for…

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

Titanyl-phthalocyanines catalytic ability towards oxygen reduction is demonstrated in experimental literature. Our recent theoretical simulations revealed electronic structure origin of catalytic ability in peripherally and axially…

Materials Science · Physics 2016-11-01 Jeffrey R. De Lile , Su Zhou

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

The electrocatalytic CO2 reduction reaction (CO2RR) is a complex multi-proton-electron transfer process that generates a vast network of reaction intermediates. Accurate prediction of free energy changes (G) of these intermediates and…

Chemical Physics · Physics 2025-04-23 Xuxin Kang , Wenjing Zhou , Ziyuan Li , Zhaoqin Chu , Hanqin Yin , Shan Gao , Aijun Du , Xiangmei Duan

Due to several attractive features, the meta-generalized-gradient approximations (meta-GGAs) are considered to be the most advanced and potentially accurate semilocal exchange-correlation functionals in the rungs of the Jacob's ladder of…

Atomic and Molecular Clusters · Physics 2020-04-28 Abhilash Patra , Subrata Jana , Lucian A. Constantin , Prasanjit Samal

The lithium manganese oxide spinel Li$_x$Mn$_2$O$_4$, with $0\leq x\leq 2$, is an important example for cathode materials in lithium ion batteries. However, an accurate description of Li$_x$Mn$_2$O$_4$ by first-principles methods like…

Materials Science · Physics 2020-05-20 Marco Eckhoff , Peter E. Blöchl , Jörg Behler

Motivated by the resurgence of electronic and optical property design in ordered fluoride and oxyfluoride compounds, we present a density functional theory (DFT) study on 19 materials with structures, ranging from simple to complex, and…

Materials Science · Physics 2016-11-23 Nenian Charles , James M. Rondinelli

We have performed a thorough computational study to assess the accuracy of density functional theory (DFT) methods in describing the interactions of CO2 with model alkali-earth-metal (AEM, Ca and Li) decorated carbon structures, namely…

Materials Science · Physics 2013-01-15 Claudio Cazorla , Stephen A. Shevlin

The antipolar $Pbcn$ phase of HfO$_2$ has been suggested to play an important role in the phase transition and polarization switching mechanisms in ferroelectric hafnia. In this study, we perform a comprehensive benchmark of density…

Materials Science · Physics 2025-03-06 Di Fan , Tianyuan Zhu , Shi Liu

In order to assess the accuracy of commonly used approximate exchange-correlation density functionals, we present a comparison of accurate exchange and correlation potentials, exchange energy densities and energy components with the…

Condensed Matter · Physics 2007-05-23 Claudia Filippi , Xavier Gonze , C. J. Umrigar

The accuracy of applying density functional theory to noncovalent interactions is hindered by errors arising from low-density regions of interaction-induced change in the density gradient, error compensation between correlation and exchange…

Chemical Physics · Physics 2014-10-22 Marcin Modrzejewski , Grzegorz Chałasiński , Małgorzata M. Szczęśniak

Most torsional barriers are predicted to high accuracy (about 1kJ/mol) by standard semilocal functionals, but a small subset has been found to have much larger errors. We create a database of almost 300 carbon-carbon torsional barriers,…

Chemical Physics · Physics 2021-02-16 Seungsoo Nam , Eunbyol Cho , Kieron Burke , Eunji Sim