A force field for bio-polymers in ionic liquids (BILFF) - part 1: [EMIm][OAc]/water mixtures

We present BILFF, a novel force field for bio-polymers in ionic liquids. In the first part of our study, we introduce optimized force field parameters for mixtures of the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([EMIm][OAc]) with water. This imidazolium-based IL is of particular practical importance as it can dissolve significant amounts of cellulose even at room temperature. An understanding of this dissolution process via molecular dynamics simulations requires a quantitative description of the microscopic structure and the strong hydrogen bonds with a method able of simulating at least several dozen nanoseconds, which is the main aim of our novel force field. To reach this goal, we optimize the force field parameters to reproduce radial, spatial, and combined distribution functions, hydrogen bond lifetimes, diffusion coefficients, and several other quantities from reference ab initio molecular dynamics (AIMD) simulations. Non-trivial effects such as dispersion interactions between the side chains and π-π stacking of the cations are reproduced very well. We further validate the force field by comparison to experimental data such as thermal expansion coefficients, bulk modulus, and density at different temperatures, which yields good agreement and correct trends. No other force field with optimized parameters for mixtures of [EMIm][OAc] and water has been presented in the literature yet. Optimized force field parameters for cellulose and other ILs will be published in upcoming articles.