Ion Pair Free Energy Surface as a Probe of Ionic Liquid Structure

TL;DR

This paper introduces a method to compare quantum mechanical and force field calculations of ion pair free energy surfaces, aiding in understanding and predicting ionic liquid structures.

Contribution

A novel approach to compare quantum and force field methods via free energy surfaces for ion pairs, improving force field parametrization for ionic liquids.

Findings

Polarizable force fields align better with DFT calculations.

Ion pair free energy surfaces reflect bulk liquid structural patterns.

Method enables higher-level comparison and refinement of force fields.

Abstract

The numerous combinations of cations and anions turn out possible to produce ionic liquids with fine-tuned properties once the correlation with the molecular structure is known. In this sense, computer simulations are useful tools to explain and even to predict properties of ionic liquids. However, quantum mechanical methods are usually restricted to either small clusters or short timescales, so that the use of parametrized force fields is needed for studying the bulk liquids. A method is proposed in this work to enable a comparison between quantum mechanical and both polarizable and non-polarizable force fields by means of the calculation of free energy surfaces for the translational motion of the anion around the cation in gas phase. This method was tested for imidazolium-based cations with 3 different anions, [BF4]-, [N(CN)2]-, and [NTf2]-. It was found better agreement with the DFT calculations when polarizability is introduced in the forcefield. In addition, the ion pair free energy surfaces reproduced the main structural patterns observed in the first coordination shell in molecular dynamics simulations of the bulk liquid, proving to be useful probes for the liquid phase structure that can be computed with higher level methods and the comparison with forcefields can indicate further improvements in their parametrization.