Thermodynamical and structural properties of imidazolium based ionic liquids from molecular simulation

We have performed molecular dynamics simulations to determine the densities and heat of vaporization as well as structural information for the 1-alkyl-3-methyl-imidazolium based ionic liquids amim]Cl] and amim]BF(4)] in the temperature range from 298 to 363 K. In this simulation study, we used an united atom model of Liu et al. Phys. Chem. Chem. Phys. 8, 1096 (2006)] for the emim(+)] and bmim(+)] cations, which we have extended for simulation in hmim]-ILs and combined with parameters of Canongia Lopes et al. J. Phys. Chem. B 108, 2038 (2004)] for the Cl(-)] anion. Our simulation results prove that both the original united atoms approach by Liu et al. and our extension yield reasonable predictions for the ionic liquid with a considerably reduced computational expense than that required for all atoms models. Radial distribution functions and spatial distribution functions where employed to analyze the local structure of this ionic liquid, and in which way it is influenced by the type of the anion, the size of the cation, and the temperature. Our simulations give evidence for the occurrence of tail aggregations in these ionic liquids with increasing length of the side chain and also increasing temperature.