Insights from Molecular Dynamics Simulations on Structural Organization and Diffusive Dynamics of an Ionic Liquid at Solid and Vacuum Interfaces

TL;DR

This study uses molecular dynamics simulations to benchmark and identify the best force field for modeling ionic liquids at interfaces, providing detailed insights into their structure and dynamics near solid and vacuum surfaces.

Contribution

It introduces a benchmarking protocol for force field selection and offers a comprehensive analysis of ionic liquid behavior at interfaces, which was previously lacking.

Findings

RESP-HF/0.9 is the optimal force field for this ionic liquid.

Detailed spatial configuration and orientation of ions at interfaces are characterized.

Interfacial stratification influences ion mobility and dynamics deep into the films.

Abstract

Hypothesis A prototypical modelling approach is required for a full characterisation of the static and equilibrium dynamical properties of confined ionic liquids (ILs), in order to gain predictive power of properties that are difficult to extract from experiments. Such a protocol needs to be constructed by benchmarking molecular dynamics simulations against available experiments. Simulations We perform an in-depth study of [C2Mim][NTf2] in bulk, at the vacuum and at hydroxylated alumina surface. Using the charge methods CHelpG, RESP-HF and RESP-B3LYP with charge scaling factors 1.0, 0.9 and 0.85, we search for an optimum non-polarizable force field by benchmarking against self-diffusion coefficients, surface tension, X-ray reflectivity data, and structural data. Findings Benchmarking, which relies on establishing the significance of an appropriate size of the model systems and the length of the simulations, yields RESP-HF/0.9 as the best suited force field for this IL overall. A complete and accurate characterisation of the spatially-dependent internal configurational space and orientation of IL molecules relative to the solid and vacuum interfaces is obtained. Furthermore, the density and mobility of IL ions in the plane parallel and normal to the interfaces is evaluated and the correlation between the stratification and dynamics in the interfacial layers is detectable deep into the films.