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research article

Accurate potential energy surfaces with a DFT plus U(R) approach

Kulik, H. J.
•
Marzari, N.  
2011
Journal of Chemical Physics

We introduce an improvement to the Hubbard U augmented density functional approach known as DFT+U that incorporates variations in the value of self-consistently calculated, linear-response U with changes in geometry. This approach overcomes the one major shortcoming of previous DFT+U studies, i.e., the use of an averaged Hubbard U when comparing energies for different points along a potential energy surface is no longer required. While DFT+U is quite successful at providing accurate descriptions of localized electrons (e.g., d or f) by correcting self-interaction errors of standard exchange correlation functionals, we show several diatomic molecule examples where this position-dependent DFT+U(R) provides a significant two- to four-fold improvement over DFT+U predictions, when compared to accurate correlated quantum chemistry and experimental references. DFT+U(R) reduces errors in binding energies, frequencies, and equilibrium bond lengths by applying the linear-response, position-dependent U(R) at each configuration considered. This extension is most relevant where variations in U are large across the points being compared, as is the case with covalent diatomic molecules such as transition-metal oxides. We thus provide a tool for deciding whether a standard DFT+U approach is sufficient by determining the strength of the dependence of U on changes in coordinates. We also apply this approach to larger systems with greater degrees of freedom and demonstrate how DFT+U(R) may be applied automatically in relaxations, transition-state finding methods, and dynamics. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3660353]

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Type
research article
DOI
10.1063/1.3660353
Author(s)
Kulik, H. J.
Marzari, N.  
Date Issued

2011

Published in
Journal of Chemical Physics
Volume

135

Issue

19

Article Number

194105

Subjects

binding energy

•

bond lengths

•

density functional theory

•

molecular

•

configurations

•

potential energy surfaces

•

quantum chemistry

•

SCF

•

calculations

•

density-functional theory

•

low-lying states

•

electronic-structure

•

transition-metal

•

cobalt carbide

•

ab-initio

•

spectroscopy

•

oxide

•

insulators

•

molecules

Editorial or Peer reviewed

REVIEWED

Written at

OTHER

EPFL units
THEOS  
Available on Infoscience
June 29, 2012
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/82952
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