ReaxFF molecular dynamics simulations on the structure and dynamics of electrolyte water systems at ambient temperature

• Published in: Computational materials science 2020-02, Vol.172 (C), p.109349, Article 109349
• Main Authors: Dasgupta, Nabankur, Kyung Shin, Yun, Fedkin, Mark V., van Duin, Adri C.T.
• Format: Article
• Language: English
• Subjects: Diffusion; Hydrogen bonds; Ions; Molecular dynamics; ReaxFF; Residence time
• ISSN: 0927-0256; 1879-0801
• DOI: 10.1016/j.commatsci.2019.109349

[Display omitted] ReaxFF molecular dynamics simulations have been performed to study the effect of cations Li+, Na+ and K+ and anion Cl− on the structural and dynamical properties of water, using the force field recently developed by Fedkin and co-workers. The structural relationship of ion and water has been analyzed from the radial distribution function and angular distribution. Comparisons of ReaxFF angle variation of ions and water within the first solvation shell were made and found to be in good agreement with literature. The disruption of hydrogen bond network of water by ions is elucidated by ion-water residence times, water-water hydrogen bond dynamics and reorientational dynamics. ReaxFF diffusion coefficient and residence times of electrolyte water system were compared with ab initio and non-reactive potentials to analyze the difference in dynamics. We gained insight into the ion interaction with water and how it can accelerate or decelerate water dynamics. ReaxFF outlines the formation and dissolution of metal hydroxides and metal chlorides over the course of simulation to explain the diffusion dynamics of water in salt solutions, allowing us to elucidate the impact of concentration on the self-diffusivity of water and ions in solutions, and to reveal that this effect always decreases the mobility and is not at all ion-specific. The obtained results have opened new opportunities to extend the ReaxFF methodology towards systems involving electrolytes.