Size dependence of cavity volume: A molecular dynamics study

Partial molar volume, V°, has been used as a tool to sample solute hydration for decades. The efficacy of volumetric investigations of hydration depends on our ability to reliably discriminate between the cavity, V C, and interaction, V I, contributions to the partial molar volume. The cavity volume, V C, consists of the intrinsic volume, V M, of a solute molecule and the thermal volume, V T, with the latter representing the volume of the effective void created around the solute. In this work, we use molecular dynamics simulations in conjunction with the Kirkwood–Buff theory to compute the partial molar volumes for organic solutes of varying sizes in water. We perform our computations using the Lennard-Jones and Coulombic pair potentials as well as truncated potentials which contain only the Lennard-Jones but not the Coulombic contribution. The partial molar volume computed with the Lennard-Jones potentials in the absence of the Coulombic term nearly coincides with the cavity volume, V C. We determine the thermal volume, V T, for each compound by subtracting its van der Waals volume, V W, from V C. Finally, we apply the spherical approximation of solute geometry to evaluate the thickness of the thermal volume, δ. Our results reveal an increase in the thickness of thermal volume, δ, with an increase in the size of the solute. This finding may be related to dewetting of large nonpolar solutes and the concomitant increase in the compressibility of water of hydration. [Display omitted] ► We use MD simulations to compute the partial molar volumes for solutes of varying sizes. ► We determine the thermal volume, V T, for each compound. ► The thickness of thermal volume increases sigmoidally with the radius of a solute.