Force field for halide and alkali ions in water based on single-ion and ion-pair thermodynamic properties for a wide range of concentrations

Author:

Duenas-Herrera Maria12ORCID,Bonthuis Douwe Jan3ORCID,Loche Philip14ORCID,Netz Roland R.1ORCID,Scalfi Laura1ORCID

Affiliation:

1. Fachbereich Physik, Freie Universität Berlin 1 , Arnimallee 14, 14195 Berlin, Germany

2. Max Planck Institute for Polymer Research 2 , Ackermannweg 10, 55128 Mainz, Germany

3. Institute of Theoretical and Computational Physics, Graz University of Technology 3 , Graz, Austria

4. Laboratory of Computational Science and Modeling, IMX, Ecole Polytechnique Federale de Lausanne 4 , 1015 Lausanne, Switzerland

Abstract

A classical non-polarizable force field for the common halide (F−, Cl−, Br−, and I−) and alkali (Li+, Na+, K+, and Cs+) ions in SPC/E water is presented. This is an extension of the force field developed by Loche et al. for Na+, K+, Cl−, and Br− (JPCB 125, 8581–8587, 2021): in the present work, we additionally optimize Lennard-Jones parameters for Li+, I−, Cs+, and F− ions. Li+ and F− are particularly challenging ions to model due to their small size. The force field is optimized with respect to experimental solvation free energies and activity coefficients, which are the necessary and sufficient quantities to accurately reproduce the electrolyte thermodynamics. Good agreement with experimental reference data is achieved for a wide range of concentrations (up to 4 mol/l). We find that standard Lorentz–Berthelot combination rules are sufficient for all ions except F−, for which modified combination rules are necessary. With the optimized parameters, we show that, although the force field is only optimized based on thermodynamic properties, structural properties are reproduced quantitatively, while ion diffusion coefficients are in qualitative agreement with experimental values.

Funder

European Research Council

Deutsche Forschungsgemeinschaft

Publisher

AIP Publishing

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