Nuclear quantum effects in water exchange around lithium and fluoride ions

TL;DR

This study uses molecular dynamics simulations to explore how nuclear quantum effects influence water exchange around lithium and fluoride ions, revealing modest quantum impacts and the importance of potential choice.

Contribution

It demonstrates the significance of nuclear quantum effects on hydration dynamics and compares classical and quantum simulation results for lithium and fluoride solutions.

Findings

Quantum effects slightly destabilize hydration shells.

Classical simulations are generally adequate for exchange mechanisms.

Quantum effects are more pronounced in lithium solutions.

Abstract

We employ classical and ring polymer molecular dynamics simulations to study the effect of nuclear quantum fluctuations on the structure and the water exchange dynamics of aqueous solutions of lithium and fluoride ions. While we obtain reasonably good agreement with experimental data for solutions of lithium by augmenting the Coulombic interactions between the ion and the water molecules with a standard Lennard-Jones ion-oxygen potential, the same is not true for solutions of fluoride, for which we find that a potential with a softer repulsive wall gives much better agreement. A small degree of destabilization of the first hydration shell is found in quantum simulations of both ions when compared with classical simulations, with the shell becoming less sharply defined and the mean residence time of the water molecules in the shell decreasing. In line with these modest differences, we find that the mechanisms of the exchange processes are unaffected by quantization, so a classical description of these reactions gives qualitatively correct and quantitatively reasonable results. We also find that the quantum effects in solutions of lithium are larger than in solutions of fluoride. This is partly due to the stronger interaction of lithium with water molecules, partly due to the lighter mass of lithium, and partly due to competing quantum effects in the hydration of fluoride, which are absent in the hydration of lithium.