Scaled-particle theory analysis of cylindrical cavities in solution.

Abstract

The solvation of hard spherocylindrical solutes is analyzed within the context of scaled-particle theory, which takes the view that the free energy of solvating an empty cavitylike solute is equal to the pressure-volume work required to inflate a solute from nothing to the desired size and shape within the solvent. Based on our analysis, an end cap approximation is proposed to predict the solvation free energy as a function of the spherocylinder length from knowledge regarding only the solvent density in contact with a spherical solute. The framework developed is applied to extend Reiss's classic implementation of scaled-particle theory and a previously developed revised scaled-particle theory to spherocylindrical solutes. To test the theoretical descriptions developed, molecular simulations of the solvation of infinitely long cylindrical solutes are performed. In hard-sphere solvents classic scaled-particle theory is shown to provide a reasonably accurate description of the solvent contact correlation and resulting solvation free energy per unit length of cylinders, while the revised scaled-particle theory fitted to measured values of the contact correlation provides a quantitative free energy. Applied to the Lennard-Jones solvent at a state-point along the liquid-vapor coexistence curve, however, classic scaled-particle theory fails to correctly capture the dependence of the contact correlation. Revised scaled-particle theory, on the other hand, provides a quantitative description of cylinder solvation in the Lennard-Jones solvent with a fitted interfacial free energy in good agreement with that determined for purely spherical solutes. The breakdown of classical scaled-particle theory does not result from the failure of the end cap approximation, however, but is indicative of neglected higher-order curvature dependences on the solvation free energy.