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Fermi‐Löwdin orbital self‐interaction corrected density functional theory: Ionization potentials and enthalpies of formation
Author(s) -
Schwalbe Sebastian,
Hahn Torsten,
Liebing Simon,
Trepte Kai,
Kortus Jens
Publication year - 2018
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.25586
Subject(s) - density functional theory , hybrid functional , ionization , chemistry , ionization energy , dissociation (chemistry) , basis set , orbital free density functional theory , fermi gamma ray space telescope , molecule , computational chemistry , atomic physics , thermodynamics , physics , quantum mechanics , ion , organic chemistry
The Fermi‐Löwdin orbital self‐interaction correction (FLO‐SIC) methodology is applied to atoms and molecules from the standard G2‐1 test set. For the first time FLO‐SIC results for the GGA‐type PBE functional are presented. In addition, examples where FLO‐SIC like any proper SIC provides qualitative improvements compared to standard DFT functionals are discussed in detail: the dissociation limit for H 2 + , the step‐wise linearity behavior for fractional occupation, as well as the significant reduction of the error of static polarizabilities. Further, ionization potentials and enthalpies of formation obtained by means of the FLO‐SIC DFT method are compared to other SIC variants and experimental values. The self‐interaction correction gives significant improvements if used with the LDA functional but shows worse performance in case of enthalpies of formation if the PBE‐GGA functional is used. The errors are analyzed and the importance of the overbinding of hydrogen is discussed. © 2018 Wiley Periodicals, Inc.