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A universal approach for continuum solvent pK a calculations: are we there yet?

  • Junming Ho
  • Michelle L. Coote
Feature Article

Abstract

This paper reviews several pK a calculation strategies that are commonly used in aqueous acidity predictions. Among those investigated were the direct or absolute method, the proton exchange scheme, and the hybrid cluster–continuum (Pliego and Riveros) and implicit–explicit (Kelly, Cramer and Truhlar) models. Additionally, these protocols are applied in the pK a calculation of 55 neutral organic and inorganic acids in conjunction with various solvent models, including the CPCM-UAKS/UAHF, IPCM, SM6 and COSMO-RS, with a view to identifying a universal approach for accurate pK a predictions. The results indicate that the direct method is unsuitable for general pK a calculations, although moderately accurate results (MAD <3 units) are possible for certain classes of acids, depending on the choice of solvent model. The proton exchange scheme generally delivers good results (MAD <2 units), with CPCM-UAKS giving the best performance. Furthermore, the sensitivity of this approach to the choice of reference acid can be substantially lessened if the solvation energies for ionic species are calculated via the IPCM cluster–continuum approach. Reference-independent hybrid approaches that include explicit water molecules can potentially give reasonably accurate values (MAD generally ~2 units) depending on the solvent model and the number of explicit water molecules added.

Keywords

Continuum solvent model pKa calculation Cluster-continuum model Proton exchange method 

Notes

Acknowledgments

We gratefully acknowledge support from the Australian Research Council under their Centres of Excellence program, and generous allocations of computing time on the National Facility of the Australian Partnership for Advanced Computing.

Supplementary material

214_2009_667_MOESM1_ESM.pdf (711 kb)
Supplementary material 1 (PDF 711 kb)
214_2009_667_MOESM2_ESM.pdf (1 mb)
Supplementary material 2 (PDF 1061 kb)

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Copyright information

© Springer-Verlag 2009

Authors and Affiliations

  1. 1.ARC Centre of Excellence for Free-Radical Chemistry and Biotechnology, Research School of ChemistryAustralian National UniversityCanberraAustralia

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