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Accurate Kohn–Sham ionization potentials from scaled‐opposite‐spin second‐order optimized effective potential methods
Author(s) -
Śmiga Szymon,
Della Sala Fabio,
Buksztel Adam,
Grabowski Ireneusz,
Fabiano Eduardo
Publication year - 2016
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.24436
Subject(s) - kohn–sham equations , density functional theory , ionization energy , context (archaeology) , physics , spin (aerodynamics) , order (exchange) , ionization , functional theory , spin density , computational chemistry , atomic physics , quantum mechanics , chemistry , condensed matter physics , thermodynamics , ion , paleontology , finance , economics , biology
One important property of Kohn–Sham (KS) density functional theory is the exact equality of the energy of the highest occupied KS orbital (HOMO) with the negative ionization potential of the system. This exact feature is out of reach for standard density‐dependent semilocal functionals. Conversely, accurate results can be obtained using orbital‐dependent functionals in the optimized effective potential (OEP) approach. In this article, we investigate the performance, in this context, of some advanced OEP methods, with special emphasis on the recently proposed scaled‐opposite‐spin OEP functional. Moreover, we analyze the impact of the so‐called HOMO condition on the final quality of the HOMO energy. Results are compared to reference data obtained at the CCSD(T) level of theory. © 2016 Wiley Periodicals, Inc.