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Comparison of second‐order orbital‐dependent DFT correlation functionals
Author(s) -
Grabowski Ireneusz
Publication year - 2008
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.21721
Subject(s) - electronic correlation , correlation , perturbation theory (quantum mechanics) , ab initio , møller–plesset perturbation theory , order (exchange) , physics , density functional theory , molecular orbital , fragment molecular orbital , statistical physics , quantum mechanics , hybrid functional , computational chemistry , molecular physics , chemistry , mathematics , molecule , geometry , finance , economics
The choice of the orbital‐dependent second‐order correlation functional plays the prime role in the description of the correlation effects in orbital‐dependent DFT calculations. Using second‐order perturbation theory we were able to derive the simplest orbital‐dependent correlation functional, but even at this lowest correlation level, we had several possibilities to define it. Applications of different second‐order correlation functionals for the atomic as well as molecular systems are presented. The ab initio DFT‐type OEP2 functionals based on Møller‐Plesset or semicanonical partitioning (OEP2‐sc) are compared with those based on Epstein‐Nesbet type partitioning, showing that the latter ones can fail in more difficult molecular problems, e.g., the Be dimer potential curve. We show that currently the best performing orbital‐dependent second‐order correlation functional is the OEP2‐sc one. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008