Homogeneous nucleation and growth in simple fluids. I. Fundamental issues and free energy surfaces of bubble and droplet formation.

The free energy of forming a droplet and a bubble with a given particle number n and volume v within the pure-component Lennard-Jones supercooled vapor and superheated liquid, respectively, are further explored using density-functional theory. Similar to what was found previously [M. J. Uline and D. S. Corti, Phys. Rev. Lett. 99, 076102 (2007); M. J. Uline and D. S. Corti, J. Chem. Phys. 129, 234507 (2008)], the limits of stability again appear within both free energy surfaces evaluated at two other metastability conditions, one closer to the binodal and one closer to the spinodal. Furthermore, an ad hoc bond connectivity criterion is also applied in an attempt, however approximately, to eliminate certain configurational redundancies that arise from the chosen droplet and bubble definitions. What results are free energy surfaces describing the formation of equilibrium embryos that should be an improved representation of the fluctuations that are relevant to those nonequilibrium embryos seen in an actual nucleation event. Finally, we discuss in some detail the use of the (n,v) reaction coordinate within the framework of an equilibrium-based theory and its relation to other descriptions of nucleation.