title: Quantum-chemistry based calibration of the alkali metal cation series (Li(+)-Cs(+)) for large-scale polarizable molecular mechanics/dynamics simulations.
abstract: 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.
authors.affiliation: Faculty of Chemistry and Pharmacy, University of Sofia, 1164 Sofia, Bulgaria.
authors.forename: Todor
authors.initials: T
authors.lastname: Dudev
authors.forename: Mike
authors.initials: M
authors.lastname: Devereux
authors.forename: Markus
authors.initials: M
authors.lastname: Meuwly
authors.forename: Carmay
authors.initials: C
authors.lastname: Lim
authors.forename: Jean-Philip
authors.initials: JP
authors.lastname: Piquemal
authors.forename: Nohad
authors.initials: N
authors.lastname: Gresh
mesh_terms: D002412:Cations / Q000737:chemistry; D008024:Ligands; D008672:Metals, Alkali / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D011789:Quantum Theory
chemical_list: D002412:Cations; D008024:Ligands; D008672:Metals, Alkali
keywords: O, N, S, and Se ligands; alkali metal cations; energy decomposition; polarizable molecular mechanics; quantum chemistry