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Radical electrophilicities in solvent

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Book cover Theoretical Chemistry in Belgium

Part of the book series: Highlights in Theoretical Chemistry ((HITC,volume 6))

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Abstract

An electrophilicity scale for radicals in solution is reported using the electrophilicity index, an important quantity in conceptual density functional theory. Five different solvents were chosen, for which the static dielectric constant covers the entire range of nonpolar to polar solvents: n-hexane (er = 1.8819), dichloromethane (er = 8.9300), 2-propanol (er = 19.2640), acetonitrile (er = 35.6880) and water (er = 78.3553). The calculations in solution were carried out within the polarizable continuum model through the Integral Equation Formalism (IEFPCM) approach. For water, also conductor-like screening model (COSMO) calculations are reported. The electronic chemical potential remains almost constant when going from gas phase to solution. However, large decreases in chemical hardness can be observed, resulting in more electrophilic radicals compared to the gas phase, and even influencing the overall order of the previously established gas-phase scale. Both solvation models (COSMO and IEF-PCM) lead to essentially the same results.

Published as part of the special collection of articles celebrating theoretical and computational chemistry in Belgium

Electronic supplementary material The online version of this article (doi:10.1007/s00214-012-1245-4) contains supplementary material, which is available to authorized users.

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Author information

Authors and Affiliations

  1. Eenheid Algemene Chemie (ALGC), Vrije Universiteit Brussel (VUB), Faculteit Wetenschappen, Pleinlaan 2, 1050, Brussels, Belgium

    Freija De Vleeschouwer, Paul Geerlings & Frank De Proft

Authors
  1. Freija De Vleeschouwer
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  2. Paul Geerlings
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  3. Frank De Proft
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Corresponding author

Correspondence to Freija De Vleeschouwer .

Editor information

Editors and Affiliations

  1. Laboratory of Theoretical Chemistry, University of Namur, Namur, Belgium

    Benoît Champagne

  2. Research Group of Theoretical Chemistry and Molecular Modeling, Hasselt University, Diepenbeek, Belgium

    Michael S. Deleuze

  3. Faculteit Wetenschappen, Free University of Brussels, Brussels, Belgium

    Frank De Proft

  4. Laboratory of Crystal Engineering Inst.of Condensed Matter and Nanoscience, Catholic University of Louvain, Louvain-La-Neuve, Belgium

    Tom Leyssens

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De Vleeschouwer, F., Geerlings, P., Proft, F.D. (2014). Radical electrophilicities in solvent. In: Champagne, B., Deleuze, M., De Proft, F., Leyssens, T. (eds) Theoretical Chemistry in Belgium. Highlights in Theoretical Chemistry, vol 6. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-41315-5_10

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