Thermodynamic properties of the ionic liquid 1-n-butyl-3-methylimidazolium hexafluorophosphate from Monte Carlo simulations

Abstract
We report results from the first molecular simulation study of 1-n-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF6], a widely studied ionic liquid. Monte Carlo simulations are carried out in the isothermal–isobaric (NPT) ensemble to calculate the molar volume, cohesive energy density, isothermal compressibility, cubic expansion coefficient and liquid structure as a function of temperature and pressure. A united atom forcefield is developed using a combination of ab initio calculations and literature parameter values. Calculated molar volumes are within 5% of experimental values, and a reasonable agreement is obtained between calculated and experimental values of the isothermal compressibility and cubic expansion coefficient. PF6 anions are found to preferentially cluster in two favorable regions near the cation.

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