The densities produced by the density functional theory: comparison to full configuration interaction

The Journal of Chemical Physics
Arteum D Bochevarov, Richard A Friesner

Abstract

We investigate one of the fundamental observables, electronic charge density, as produced by a number of popular functionals of the density functional theory (DFT): SVWN5, B3LYP, B3LYP, OLYP, O3LYP, BP86, B3P86, O3P86, and PBE using restricted and unrestricted orbitals. Measuring and comparing the quality of the densities could tell us more about the physical soundness of the functional models. The study is performed on the small molecules He, H2, LiH, H4 in an extensive range of correlation-consistent basis sets. We compare DFT densities to those of full configuration interaction (FCI) under the assumption that the FCI density in the largest employed basis set is sufficiently close to the exact one. For LiH and H4, we also compare the DFT densities to those of CCSD. The SVWN5 functional consistently shows the worst performance. The OPTX exchange functional regularly beats the Becke exchange. Among the best performers are all the hybrid functionals, the novel O3P86 being the most accurate in most cases. The popular functional B3LYP was consistently outmatched by O3LYP, and produced, in fact, some of the poorest densities among the hybrids. CCSD was found to produce much more accurate densities than any DFT functional in the cas...Continue Reading

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Citations

Jan 29, 2009·The Journal of Chemical Physics·T Martín-BlasJ E Alvarellos
Jan 17, 2013·The Journal of Chemical Physics·Vincent Tognetti, Laurent Joubert
Aug 14, 2009·The Journal of Chemical Physics·Deborah L Crittenden, Yves A Bernard
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Nov 24, 2017·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Jasper AdamsonRiina Aav
May 22, 2021·The Journal of Physical Chemistry. a·Carlos Martín-Fernández, Jeremy N Harvey
Jan 25, 2011·Journal of Chemical Theory and Computation·Arteum D BochevarovStephen J Lippard
Jan 4, 2018·Journal of Chemical Theory and Computation·Qing Zhao, Heather J Kulik
Dec 14, 2016·Journal of Chemical Theory and Computation·Terry Z H Gani, Heather J Kulik
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Nov 19, 2019·Journal of Chemical Theory and Computation·Fang Liu, Heather J Kulik
Aug 26, 2021·Journal of Computational Chemistry·Mirosław Jabłoński, Tadeusz M Krygowski

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Software Mentioned

PSI
DFT
O3LYP
OLYP
O3P86
BLYP
SPW91

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