title: Influence of small rings on the thermodynamics of equilibrium self-assembly.
abstract: The competition between the formation of linear chain clusters and ring structures in an equilibrium self-assembling system is reexamined by developing a new Flory-Huggins type theory that combines an estimate for the loss of configurational entropy ΔS(ring) upon ring formation with the standard treatment of the free energy of a polydisperse solution of linear chains. The excess entropy of ring formation ΔS(ring) is obtained from an analytical fit to exact enumeration data for self-avoiding chains and rings with 30 or fewer steps on a cubic lattice. Illustrative calculations of the spinodal curves and the extent and the average degree of self-assembly highlight the physical conditions for which the cyclic structures impact the thermodynamic characterization of equilibrium self-assembling systems.
authors: James Franck Institute and Department of Chemistry, University of Chicago, Chicago, Illinois 60637, USA.
authors: Karl F
authors: KF
authors: Freed
mesh_terms: D006863:Hydrogen-Ion Concentration; D008962:Models, Theoretical; D012996:Solutions; D013816:Thermodynamics
chemical_list: D012996:Solutions