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Impact of non‐empirically tuning the range‐separation parameter of long‐range corrected hybrid functionals on ionization potentials, electron affinities, and fundamental gaps
Author(s) -
Vikramaditya Talapunur,
Chai JengDa,
Lin ShiangTai
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.25575
Subject(s) - affinities , electron affinity (data page) , range (aeronautics) , ionization energy , homo/lumo , ionization , electron , reciprocal , chemistry , bohr model , computational chemistry , atomic physics , statistical physics , physics , materials science , quantum mechanics , ion , molecule , stereochemistry , linguistics , philosophy , composite material
Non‐empirically tuning the range‐separation parameter (ω) of long‐range corrected (LC) hybrid functionals in improving the accuracy of vertical ionization potentials (IPs), vertical electron affinities (EAs), and fundamental gaps (FGs) is investigated. Use of default ω values gives the best overall property predictions employing the Δ self‐consistent field (ΔSCF) approach, if sufficiently large basis set is used. Upon tuning, IP (HOMO) (i.e., the IP estimated from the negative of HOMO energy via DFT Koopmans’ theorem) with the IP (ΔSCF) (i.e., the IP obtained from the ΔSCF approach) the accuracy of IP (HOMO) significantly improves however a reciprocal phenomenon is not observed. An interesting observation is that EA (LUMO) (i.e., the EA estimated from the negative of LUMO energy) is more accurate than EA (ΔSCF), if the ω value is in the range of 0.30 to 0.50 bohr −1 . © 2018 Wiley Periodicals, Inc.