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Journal of Chemical Physics / Volume 131 / Issue 23 / COMMUNICATIONS
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J. Chem. Phys. 131, 231101 (2009); doi:10.1063/1.3269030 (4 pages)

Koopmans’ springs to life

Ulrike Salzner1 and Roi Baer2

1Department of Chemistry, Bilkent University, 06800 Bilkent, Ankara, Turkey
2Fritz Haber Center for Molecular Dynamics, Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel

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(Received 27 June 2009; accepted 9 November 2009; published online 16 December 2009)

The meaning of orbital energies (OOEs) in Kohn–Sham (KS) density functional theory (DFT) is subject to a longstanding controversy. In local, semilocal, and hybrid density functionals (DFs) a Koopmans’ approach, where OOEs approximate negative ionization potentials (IPs), is unreliable. We discuss a methodology based on the Baer–Neuhauser–Livshits range-separated hybrid DFs for which Koopmans’ approach “springs to life.” The OOEs are remarkably close to the negative IPs with typical deviances of ±0.3 eV down to IPs of 30 eV, as demonstrated on several molecules. An essential component is the ab initio motivated range-parameter tuning procedure, forcing the highest OOE to be exactly equal to the negative first IP. We develop a theory for the curvature of the energy as a function of fractional occupation numbers to explain some of the results.

© 2009 American Institute of Physics

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KEYWORDS and PACS

Keywords

ab initio calculations, density functional theory, orbital calculations

PACS

ARTICLE DATA

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http://link.aip.org/link/doi/10.1063/1.3269030

PUBLICATION DATA

ISSN:

0021-9606 (print)  
1089-7690 (online)

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$abstract.society.value is a Member of CrossRef American Institute of Physics

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Figures (click on thumbnails to view enlargements)

FIG.1
Deviance of negative OOEs and SCF/TD energies relative to vertical IPs derived from experiment data (Refs. 50 , 51 , 52) for several molecules. KS and SAOP OOEs data are taken from Ref. 9.

FIG.1 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

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