We present and test a new approximation for the exchange-correlation (xc) energy of Kohn-Sham density functional theory. It combines exact exchange with a compatible non-local correlation functional. The functional is by construction free of one-electron self-interaction, respects constraints derived from uniform coordinate scaling, and has the correct asymptotic behavior of the xc energy density. It contains one parameter that is not determined ab initio. We investigate whether it is possible to construct a functional that yields accurate binding energies and affords other advantages, specifically Kohn-Sham eigenvalues that reliably reflect ionization potentials. Tests for a set of atoms and small molecules show that within our local-hybrid form accurate binding energies can be achieved by proper optimization of the free parameter in our functional, along with an improvement in dissociation energy curves and in Kohn-Sham eigenvalues. However, the correspondence of the latter to experimental ionization potentials is not yet satisfactory, and if we choose to optimize their prediction, a rather different value of the functional's parameter is obtained. We put this finding in a larger context by discussing similar observations for other functionals and possible directions for further functional development that our findings suggest.
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14 May 2014
Research Article|
February 24 2014
A self-interaction-free local hybrid functional: Accurate binding energies vis-à-vis accurate ionization potentials from Kohn-Sham eigenvalues
Tobias Schmidt;
Tobias Schmidt
a)
1Theoretical Physics IV,
University of Bayreuth
, 95440 Bayreuth, Germany
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Eli Kraisler;
Eli Kraisler
a)
2Department of Materials and Interfaces,
Weizmann Institute of Science
, Rehovoth 76100, Israel
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Adi Makmal;
Adi Makmal
b)
2Department of Materials and Interfaces,
Weizmann Institute of Science
, Rehovoth 76100, Israel
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Leeor Kronik;
Leeor Kronik
2Department of Materials and Interfaces,
Weizmann Institute of Science
, Rehovoth 76100, Israel
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Stephan Kümmel
Stephan Kümmel
1Theoretical Physics IV,
University of Bayreuth
, 95440 Bayreuth, Germany
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J. Chem. Phys. 140, 18A510 (2014)
Article history
Received:
November 15 2013
Accepted:
February 04 2014
Citation
Tobias Schmidt, Eli Kraisler, Adi Makmal, Leeor Kronik, Stephan Kümmel; A self-interaction-free local hybrid functional: Accurate binding energies vis-à-vis accurate ionization potentials from Kohn-Sham eigenvalues. J. Chem. Phys. 14 May 2014; 140 (18): 18A510. https://doi.org/10.1063/1.4865942
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