Solubilities of pyrene in organic solvents: Comparison between chemical potential calculations using a cavity-based method and direct coexistence simulations
Journal of Chemical Thermodynamics
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Wand, C., Fayaz-Torshizi, M., Jiménez-Serratos, G., Müller, E., & Frenkel, D. (2019). Solubilities of pyrene in organic solvents: Comparison between chemical potential calculations using a cavity-based method and direct coexistence simulations. Journal of Chemical Thermodynamics, 131 620-629. https://doi.org/10.1016/j.jct.2018.11.029
In this paper, we benchmark a cavity-based simulation method for calculating the relative solubility of large molecules in explicit solvents. The essence of the procedure is the accounting of the Gibbs energy change associated with an alchemical thermodynamic cycle where, in sequence, a cavity is created in a solvent, a solute is inserted in the cavity and the cavity is annihilated. The Gibbs energy change is equated to the excess chemical potential allowing the comparison of solubilities in different solvents. The results obtained using the cavity-based method are compared to direct large-scale molecular dynamics simulations performed using coarse-grained models for calculating the partition coefficient of pyrene between heptane and toluene. We demonstrate the applicability of this cavity-based technique under high pressure/temperature conditions.
The authors gratefully acknowledge the generous funding and technical support for this work from BP Plc through the International Centre for Advanced Materials (ICAM) which made this research possible.
External DOI: https://doi.org/10.1016/j.jct.2018.11.029
This record's URL: https://www.repository.cam.ac.uk/handle/1810/289767