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The role of the long‐range exchange corrections in the description of electron delocalization in aromatic species
Author(s) -
Szczepanik Dariusz W.,
Solà Miquel,
Andrzejak Marcin,
Pawełek Barbara,
Dominikowska Justyna,
Kukułka Mercedes,
Dyduch Karol,
Krygowski Tadeusz M.,
Szatylowicz Halina
Publication year - 2017
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.24805
Subject(s) - aromaticity , delocalized electron , electron delocalization , electron , computational chemistry , range (aeronautics) , electron exchange , benchmark (surveying) , chemistry , chemical physics , physics , materials science , molecule , quantum mechanics , organic chemistry , geodesy , composite material , geography
In this article, we address the role of the long‐range exchange corrections in description of the cyclic delocalization of electrons in aromatic systems at the density functional theory level. A test set of diversified monocyclic and polycyclic aromatics is used in benchmark calculations involving various exchange‐correlation functionals. A special emphasis is given to the problem of local aromaticity in acenes, which has been a subject of long‐standing debate in the literature. The presented results indicate that the noncorrected exchange‐correlation functionals significantly overestimate cyclic delocalization of electrons in heteroaromatics and aromatic systems with fused rings, which in the case of acenes leads to conflicting local aromaticity predictions from different criteria. © 2017 Wiley Periodicals, Inc.