Thermodynamic and Transport Properties of Crown-Ethers: Force Field Development and Molecular Simulations

Crown-ethers have recently been used to assemble porous liquids (PLs), which are liquids with permanent porosity formed by mixing bulky solvent molecules (e.g., 15-crown-5 ether) with solvent-inaccessible organic cages. PLs and crown-ethers belong to a novel class of materials, which can potentially be used for gas separation and storage, but their performance for this purpose needs to be assessed thoroughly. Here, we use molecular simulations to study the gas separation performance of crown-ethers as the solvent of porous liquids. The TraPPE force field for linear ether molecules has been adjusted by fitting a new set of torsional potentials to accurately describe cyclic crown-ether molecules. Molecular dynamics (MD) simulations have been used to compute densities, shear viscosities, and self-diffusion coefficients of 12-crown-4, 15-crown-5, and 18-crown-6 ethers. In addition, Monte Carlo (MC) simulations have been used to compute the solubility of the gases CO2, CH4, and N2 in 12-crown-4 and 15-crown-5 ether. The computed properties are compared with available experimental data of crown-ethers and their linear counterparts, i.e., polyethylene glycol dimethyl ethers.