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Isodesmic reaction for pK a calculations of common organic molecules

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Book cover 8th Congress on Electronic Structure: Principles and Applications (ESPA 2012)

Part of the book series: Highlights in Theoretical Chemistry ((HITC,volume 5))

Abstract

Three quantum chemistry methods (B3LYP, M05-2X and CBS-4B3*) have been used, in combination with SMD and CPCM continuum solvent models, to calculate the aqueous pKa values of common organic compounds (aliphatic alcohols, carboxylic acids, amines, phenols, benzoic acids and pyridines) by using an isodesmic reaction. Good precision is found for all the studied functional groups, resulting mean absolute deviations of 0.5–1 pKa units (equivalent to the best results obtained with thermodynamic cycles). It is worthy to note that no explicit water molecules were needed with the isodesmic reaction. In addition, the quality of the results is not strongly dependent on the combination of quantum chemistry method, solvent model and reference species. Therefore, the isodesmic reaction could be successfully used when dealing with gas-phase unstable species, with species that undergo large conformational changes between gas-phase and solution-phase or other difficult cases for the thermodynamic cycles.

Published as part of the special collection of articles derived from the 8th Congress on Electronic Structure: Principles and Applications (ESPA 2012).

Electronic supplementary material The online version of this article (doi:10.1007/s00214-012-1310-z) contains supplementary material, which is available to authorized users.

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Authors and Affiliations

  1. Institut d’Investigació en Ciènces de la Salut (IUNICS), Departament de Química, Universitat de les Illes Balears, 07122, Palma de Mallorca, Spain

    Sebastián Sastre, Rodrigo Casasnovas, Francisco Muñoz & Juan Frau

Authors
  1. Sebastián Sastre
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  2. Rodrigo Casasnovas
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  3. Francisco Muñoz
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  4. Juan Frau
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Correspondence to Juan Frau .

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Editors and Affiliations

  1. Facultat de Química Dept. de Química Física & IQTCUB, Universitat de Barcelona, Barcelona, Spain

    Juan J. Novoa

  2. SRSMC, Theoret. Chemistry and Biochem. Group, University of Lorraine, Vandoeuvre-les-Nancy, France

    Manuel F. Ruiz López

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Sastre, S., Casasnovas, R., Muñoz, F., Frau, J. (2014). Isodesmic reaction for pK a calculations of common organic molecules. In: Novoa, J., Ruiz López, M. (eds) 8th Congress on Electronic Structure: Principles and Applications (ESPA 2012). Highlights in Theoretical Chemistry, vol 5. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-41272-1_7

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