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Towards a converged strategy for including microsolvation in reaction mechanism calculations

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Abstract

A major part of chemical conversions is carried out in the fluid phase, where an accurate modeling of the involved reactions requires to also take into account solvation effects. Implicit solvation models often cover these effects with sufficient accuracy but can fail drastically when specific solvent–solute interactions are important. In those cases, microsolvation, i.e., the explicit inclusion of one or more solvent molecules, is a commonly used strategy. Nevertheless, microsolvation also introduces new challenges—a consistent workflow as well as strategies how to systematically improve prediction performance are not evident. For the COSMO and COSMO-RS solvation models, this work proposes a simple protocol to decide if microsolvation is needed and how the corresponding molecular model has to look like. To demonstrate the improved accuracy of the approach, specific application examples are presented and discussed, i.e., the computation of aqueous pKa values and a mechanistic study of the methanol mediated Morita–Baylis–Hillman reaction.

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Acknowledgements

The authors thank Stefan Grimme for providing the code to compute the vibrational entropy with the quasi-rigid-rotor-harmonic-oscillator approach, Oliver Welz and Mikko Muuronen for helpful discussions, and the reviewers for their thorough work.

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Author notes

  1. Moad el Mahdali

    Present address: Institut de Quimica Computacional i Catalisi, Universitat de Girona, c/M Aurelia Capmany 69, Girona, 17003, Spain

Authors and Affiliations

  1. BASF SE, Carl-Bosch-Strasse 38, 67056, Ludwigshafen am Rhein, Germany

    Rebecca Sure, Moad el Mahdali, Alex Plajer & Peter Deglmann

  2. Department of Chemistry, University of Oxford, OX1 3TF, Oxford, UK

    Alex Plajer

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  1. Rebecca Sure
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Contributions

MM and AP carried out preliminary studies. PD performed the computations for the introduction and the section “general strategy” and RS performed those for the acid–base reactions and the MBH mechanism. RS and PD wrote the manuscript.

Corresponding author

Correspondence to Rebecca Sure.

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Sure, R., el Mahdali, M., Plajer, A. et al. Towards a converged strategy for including microsolvation in reaction mechanism calculations. J Comput Aided Mol Des 35, 473–492 (2021). https://doi.org/10.1007/s10822-020-00366-2

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