RESUMO
We present the extension of our force field BILFF (Bio-Polymers in Ionic Liquids Force Field) to the bio-polymer cellulose. We already published BILFF parameters for mixtures of ionic liquid 1-ethyl-3-methylimidazolium acetate ([EMIm][OAc]) with water. Our all-atom force field focuses on a quantitative reproduction of the hydrogen bonds in the complex mixture of cellulose, [EMIm]+, [OAc]- and water when compared to reference ab initio molecular dynamics (AIMD) simulations. To enhance the sampling, 50 individual AIMD simulations starting from different initial configurations were performed for cellulose in solvent instead of one long simulation, and the resulting averages were used for force field optimization. All cellulose force field parameters were iteratively adjusted starting from the literature force field of W. Damm et al. We were able to obtain a very good agreement with respect to both the microstructure of the reference AIMD simulations and experimental results such as the system density (even at higher temperatures) and the crystal structure. Our new force field allows performing very long simulations of large systems containing cellulose solvated in (aqueous) [EMIm][OAc] with almost ab initio accuracy.
RESUMO
We present an extension of our previously developed all-atom force field BILFF (Bio-polymers in Ionic Liquids Force Field) to three different ionic liquids: 1-ethyl-3-methyl-1,2,3-triazolium acetate ([EMTr][OAc]), 1-ethyl-3-methyl-1,2,3-triazolium benzoate ([EMTr][OBz]), and 1-ethyl-3-methylimidazolium benzoate ([EMIm][OBz]). These ionic liquids are of practical importance as they have the ability to dissolve significant amounts of cellulose even at room temperature. Our force field is optimized to accurately reproduce the strong hydrogen bonding in the system with nearly quantum chemical accuracy. A very good agreement between the microstructure of the quantum chemical simulations over a wide temperature range and experimental density data with the results of BILFF were observed. Non-trivial effects, such as the solvation shell structure and π-π stacking of the cations, are also accurately reproduced. Our force field enables accurate simulations of larger systems, such as solvated cellulose in different (aqueous) ionic liquids, and is the first to present the optimized parameters for mixtures of these solvents and water.
RESUMO
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.