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The linear response kernel of conceptual DFT as a measure of aromaticity

We continue a series of papers in which the chemical importance of the linear response kernel chi(r, r’) of conceptual DFT is investigated. In previous contributions (J. Chem. Theory Comput. 2010, 6, 3671; J. Phys. Chem. Lett. 2010, 1, 1228; Chem. Phys. Lett. 2010, 498, 192), two computational methodologies were presented and it was observed that the linear response kernel could serve as a measure of electron delocalisation, discerning inductive, resonance and hyperconjugation effects. This study takes the analysis one step further, linking the linear response kernel to the concept of aromaticity. Based on a detailed analysis of a series of organic and inorganic (poly) cyclic molecules, we show that the atom-condensed linear response kernel discriminates between aromatic and non-aromatic systems. Moreover, a new quantitative measure of aromaticity, termed the para linear response (PLR) index, is introduced. Its definition was inspired by the recent work published around the para delocalisation index (PDI). Both indices are shown to correlate very well, which emphasises the linear response kernel’s value in the theoretical description of aromaticity

The authors thank Jens Top for performing preliminary calculations. N. S. acknowledges the Research Foundation-Flanders (FWO) for a position as research assistant. F. D. P. and P. G. thank the FWO and the Vrije Universiteit Brussel for continuous financial support. M. S. thanks the Spanish MICINN (CTQ2008-03077/BQU and CTQ2011-23156 projects) and the Catalan DIUE (2009SGR637 and ICREA Academia 2009 prize)

Royal Society of Chemistry (RSC)

Manager: Ministerio de Ciencia e Innovación (Espanya)
Author: Sablon, Nick
De Proft, Frank
Solà i Puig, Miquel
Geerlings, Paul
Abstract: We continue a series of papers in which the chemical importance of the linear response kernel chi(r, r’) of conceptual DFT is investigated. In previous contributions (J. Chem. Theory Comput. 2010, 6, 3671; J. Phys. Chem. Lett. 2010, 1, 1228; Chem. Phys. Lett. 2010, 498, 192), two computational methodologies were presented and it was observed that the linear response kernel could serve as a measure of electron delocalisation, discerning inductive, resonance and hyperconjugation effects. This study takes the analysis one step further, linking the linear response kernel to the concept of aromaticity. Based on a detailed analysis of a series of organic and inorganic (poly) cyclic molecules, we show that the atom-condensed linear response kernel discriminates between aromatic and non-aromatic systems. Moreover, a new quantitative measure of aromaticity, termed the para linear response (PLR) index, is introduced. Its definition was inspired by the recent work published around the para delocalisation index (PDI). Both indices are shown to correlate very well, which emphasises the linear response kernel’s value in the theoretical description of aromaticity
The authors thank Jens Top for performing preliminary calculations. N. S. acknowledges the Research Foundation-Flanders (FWO) for a position as research assistant. F. D. P. and P. G. thank the FWO and the Vrije Universiteit Brussel for continuous financial support. M. S. thanks the Spanish MICINN (CTQ2008-03077/BQU and CTQ2011-23156 projects) and the Catalan DIUE (2009SGR637 and ICREA Academia 2009 prize)
Format: application/pdf
Document access: http://hdl.handle.net/10256/11418
Language: eng
Publisher: Royal Society of Chemistry (RSC)
Collection: info:eu-repo/semantics/altIdentifier/doi/10.1039/c2cp23372j
info:eu-repo/semantics/altIdentifier/issn/1463-9076
info:eu-repo/semantics/altIdentifier/eissn/1463-9084
info:eu-repo/grantAgreement/MICINN//CTQ2011-23156/ES/AVANCES EN CATALISIS Y AROMATICIDAD/
info:eu-repo/grantAgreement/MICINN//CTQ2008-03077/ES/CLUSTERES METALICOS Y SEMIMETALICOS. ESTUDIOS DE AROMATICIDAD Y REACTIVIDAD/
Rights: Tots els drets reservats
Subject: Aromaticitat (Química)
Aromaticity (Chemistry)
Funcional de densitat, Teoria del
Density functionals
Kernel, Funcions de
Kernel functions
Title: The linear response kernel of conceptual DFT as a measure of aromaticity
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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