Computational Study of Volumetric Effects of Hydration

Computational Study of Volumetric Effects of Hydration Molecular Dynamics (MD) simulations were used in conjunction with the Kirkwood-Buff (KB) theory to compute partial molar volume (PMV) for solutes of various chemical natures. Simulations performed with only the Lennard-Jones (LJ) potential yield PMV for solutes which coincide with the cavity volumes derived from calculations with scaled particle theory (SPT). Whereas, simulations carried out with only the repulsive LJ term produced PMV of solutes closer to their excluded volumes. We also determined the thermal volume, V T , which represents the volume of the effective void created around solutes of varying cavity sizes and applied the spherical approximation of solute geometry to evaluate the thickness of the thermal volume, . Our results reveal an increase in the thickness of thermal volume, , with an increase in the size of the solute. Our theoretical results are in good agreement with the reported empirical schemes for parsing PMV data on small solutes. iii Dedication To my beloved grandfather, Savjibhai, my loving parents, Ashok and Smita and my brother, Raj.