Quantum‐chemistry based calibration of the alkali metal cation series (Li+Cs+) for large‐scale polarizable molecular mechanics/dynamics simulations

The alkali metal cations in the series Li+Cs+ act as major partners in a diversity of biological processes and in bioinorganic chemistry. In this article, we present the results of their calibration in the context of the SIBFA polarizable molecular mechanics/dynamics procedure. It relies on quantum‐chemistry (QC) energy‐decomposition analyses of their monoligated complexes with representative O, N, S, and Se ligands, performed with the aug‐cc‐pVTZ(‐f) basis set at the Hartree–Fock level. Close agreement with QC is obtained for each individual contribution, even though the calibration involves only a limited set of cation‐specific parameters. This agreement is preserved in tests on polyligated complexes with four and six O ligands, water and formamide, indicating the transferability of the procedure. Preliminary extensions to density functional theory calculations are reported.

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