Publication: Coarse-grained Hamiltonian and effective one component theory of colloidal suspensions
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Date
2022
Authors
Journal Title
Journal of Molecular Liquids
Journal ISSN
Volume Title
Publisher
Elsevier B.V.
Abstract
We develop a theory to trace out the solvent degrees of freedom from the grand partition function of colloid-solvent mixtures. Our approach to coarse-graining is based on density functional formalism of density profile and the grand thermodynamic potential of solvent. The solvent-induced interaction which is many-body in character is expressed in terms of two functionals; one that couples the solvent to the colloidal density distribution and the second represents the density�density correlation function of the solvent. The nature, strength, and range of the potential depend on these functionals and therefore on the thermodynamic state of the solvent. The solvent-induced contribution to free energy functional is also derived. A self-consistent procedure is developed to calculate the effective potential between colloidal particles, colloid-solvent, and colloid-colloid correlation functions. The theory is used to investigate both additive and nonadditive binary hard-sphere mixtures. Results are reported for the two systems for several values of packing fractions ?b and ?s and particles diameter ratio [Formula presented] where symbols b and s refer to colloid and solvent, respectively. Several interesting features are found: The short-range attractive part of the potential shows non-monotonic dependence on ?b; when ?b is increased from zero, initially the potential becomes more attractive but beyond a certain value of ?b that depends on q, the attraction starts weakening. The repulsive peaks formed at [Formula presented] where R is a distance between centers of colloidal particles expressed in units of ?b and n is an integer, become stronger on increasing ?b. These results show that many-body contribution to the effective potential depends in a subtle way on packing fractions ?b,?s, size ratio q, and on nature of the interaction model and makes a non-negligible contribution to the coarse-grained Hamiltonian. � 2022 Elsevier B.V.
Description
Keywords
Coarse-graining, Colloidal suspensions, Effective Hamiltonian, Effective interactions, Many-body effect