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Rules of Aromaticity

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Applications of Topological Methods in Molecular Chemistry

Part of the book series: Challenges and Advances in Computational Chemistry and Physics ((COCH,volume 22))

Abstract

The concept of aromaticity is elusive; it is not directly observable. Somewhat surprisingly, given the fuzzy character of this concept, there exist a number of very simple mathematical rules that can account for the aromaticity of a large number of organic and inorganic molecules. Among them we can mention Hückel’s, Baird’s, Wade-Mingos’, and Hirsch’s rules. In this chapter we summarize recent advances carried out in our group in the study of these aromaticity rules.

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Notes

  1. 1.

    The ground-state minimal energy structure of COT is a non-aromatic and non-planar species that is not so interesting from Baird's rule perspective. For this reason, we have chosen the planar D 4h COT, which is not an energy minimum but is a stationary point of the potential energy surface with bond-length alternation and well-known antiaromatic character.

  2. 2.

    B3LYP also includes some electron correlation effects in the calculation of the energy but it is a well-documented fact that the use of Kohn-Sham wavefunction to calculate the electron delocalization indices provides results close to the Hartree-Fock ones and, therefore, they do not include electron correlation [45].

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Acknowledgments

This work has been supported by the Ministerio de Economía y Competitividad (MINECO) of Spain (Projects CTQ2014-54306-P and CTQ2013-41236-ERC) and the Generalitat de Catalunya (project 2014SGR931, Xarxa de Referència en Química Teòrica i Computacional, and ICREA Academia 2014 prize for M.S.). F.F. acknowledges financial support of the Beatriu de Pinós programme from AGAUR for the postdoctoral grants BP_A_00339 and BP_A2_00022. The EU under the Marie Curie Career Integration grant PCI09-GA-2011-294240 (E.M.) and the FEDER grant UNGI10-4E-801 (European Fund for Regional Development) have also funded this research.

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Authors and Affiliations

  1. Institut de Química Computational I Catàlisi and Departament de Química, Universitat de Girona, Campus de Montilivi, 17071, Girona, Catalonia, Spain

    Ferran Feixas, Eduard Matito & Miquel Solà

  2. Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, Vrije Universiteit, De Boelelaan 1083, NL-1081HV, Amsterdam, The Netherlands

    Jordi Poater

Authors
  1. Ferran Feixas
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  2. Eduard Matito
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  3. Jordi Poater
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  4. Miquel Solà
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Correspondence to Miquel Solà .

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Editors and Affiliations

  1. LCC-CNRS, Toulouse, France

    Remi Chauvin

  2. LCC-CNRS, Toulouse, France

    Christine Lepetit

  3. Théorique, UMR 761, Laboratoire de Chimie, Paris, France

    Bernard Silvi

  4. CNRS/UPM, MONARIS UMR 8233 (LADIR + LM2N), Paris, France

    Esmail Alikhani

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Feixas, F., Matito, E., Poater, J., Solà, M. (2016). Rules of Aromaticity. In: Chauvin, R., Lepetit, C., Silvi, B., Alikhani, E. (eds) Applications of Topological Methods in Molecular Chemistry. Challenges and Advances in Computational Chemistry and Physics, vol 22. Springer, Cham. https://doi.org/10.1007/978-3-319-29022-5_12

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