Development of a MOF-FF-compatible interaction model for liquid methanol and Cl− in methanol

If complex systems are to be studied in molecular simulation, one usually attempts to combine existing interaction models in order to describe the new system. This is, however, not always feasible. We thus propose here a new pairwise-additive interaction model for liquid methanol and solvated Cl− to be used to study the immersion of Metal-Organic Frameworks (MOFs) in methanol. Practically, it entails that all interactions must be written to be compatible with the family of MOF-FF models, which have been specifically developed and then widely employed in molecular simulations of such MOFs, in particular flexible ones. The new model for liquid methanol has been mostly tailored to provide densities and dielectric constants as close to experiment as possible in a large temperature domain. This is important since the flexible MOFs modify their shapes according to their loading with guest molecules of various types, and also according to the thermodynamic conditions. The model yields excellent agreement for the density-temperature, dielectric constant-temperature, and self-diffusion-temperature relationships, properties. Other properties such as e.g. the compressibilities or thermal expansion coefficients are of the correct order of magnitude. Since some MOF frameworks are electrically charged, counterions will be present in these cases. The interactions of Cl− with the liquid are thus also considered here. The solvation of this ion is also found to be satisfactory when compared to other MD studies.