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.