Item


The role of the long-range exchange corrections in the description of electron delocalization in aromatic species

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

The research was supported in part by the Foundation for Polish Science (FNP START 2015, stipend 103.2015, DS), National Science Centre, Poland (NCN SONATA, grant 2015/17/D/ST4/ 00558, DS) as well as the PL-Grid Infrastructure of the Academic Computer Centre CYFRONET, with the calculations performed on cluster platforms Zeus and Prometheus. MS thanks for the support of the Ministerio de Economía y Competitividad of Spain (Project CTQ2014-54306-P), Generalitat de Catalunya (project number 2014SGR931, Xarxa de Referència en Química Teòrica i Computacional, and ICREA Academia prize), and European Fund for Regional Development (FEDER grant UNGI10-4E-801)

© Journal of Computational Chemistry, 2017, vol. 38, núm. 18, p. 1640-1654

Wiley

Manager: Ministerio de Economía y Competitividad (Espanya)
Author: Szczepanik, Dariusz W.
Solà i Puig, Miquel
Andrzejak, Marcin
Pawełek, Barbara
Dominikowska, Justyna
Kukułka, Mercedes
Dyduch, Karol
Krygowski, Tadeusz M.
Szatylowicz, Halina
Date: 2017 July 5
Abstract: 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
The research was supported in part by the Foundation for Polish Science (FNP START 2015, stipend 103.2015, DS), National Science Centre, Poland (NCN SONATA, grant 2015/17/D/ST4/ 00558, DS) as well as the PL-Grid Infrastructure of the Academic Computer Centre CYFRONET, with the calculations performed on cluster platforms Zeus and Prometheus. MS thanks for the support of the Ministerio de Economía y Competitividad of Spain (Project CTQ2014-54306-P), Generalitat de Catalunya (project number 2014SGR931, Xarxa de Referència en Química Teòrica i Computacional, and ICREA Academia prize), and European Fund for Regional Development (FEDER grant UNGI10-4E-801)
Format: application/pdf
Citation: https://doi.org/10.1002/jcc.24805
ISSN: 0192-8651 (versió paper)
1096-987X (versió electrònica)
Document access: http://hdl.handle.net/10256/14344
Language: eng
Publisher: Wiley
Collection: MINECO/PE 2015-2017/CTQ2014-54306-P
Reproducció digital del document publicat a: https://doi.org/10.1002/jcc.24805
Articles publicats (D-Q)
Is part of: © Journal of Computational Chemistry, 2017, vol. 38, núm. 18, p. 1640-1654
Rights: Tots els drets reservats
Subject: Aromaticitat (Química)
Aromaticity (Chemistry)
Funcional de densitat, Teoria del
Density functionals
Title: The role of the long-range exchange corrections in the description of electron delocalization in aromatic species
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

Subjects

Authors