Polymorph Stability and Free Energy of Crystallization of Freely-Jointed Polymers of Hard Spheres.

ABSTRACT: The free energy of crystallization of monomeric hard spheres as well as their thermodynamically stable polymorph have been known for several decades. In this work, we present semianalytical calculations of the free energy of crystallization of freely-jointed polymers of hard spheres as well as of the free energy difference between the hexagonal closed packed (HCP) and face-centered cubic (FCC) polymorphs. The phase transition (crystallization) is driven by an increase in translational entropy that is larger than the loss of conformational entropy of chains in the crystal with respect to chains in the initial amorphous phase. The conformational entropic advantage of the HCP polymer crystal over the FCC one is found to be ΔschHCP-FCC≈0.331×10-5k per monomer (expressed in terms of Boltzmann's

SUBMITTER: Herranz M 

PROVIDER: S-EPMC10058036 | biostudies-literature | 2023 Mar

REPOSITORIES: biostudies-literature