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Title: Reference interaction site model and optimized perturbation theories of colloidal dumbbells with increasing anisotropy

We investigate thermodynamic properties of anisotropic colloidal dumbbells in the frameworks provided by the Reference Interaction Site Model (RISM) theory and an Optimized Perturbation Theory (OPT), this latter based on a fourth-order high-temperature perturbative expansion of the free energy, recently generalized to molecular fluids. Our model is constituted by two identical tangent hard spheres surrounded by square-well attractions with same widths and progressively different depths. Gas-liquid coexistence curves are obtained by predicting pressures, free energies, and chemical potentials. In comparison with previous simulation results, RISM and OPT agree in reproducing the progressive reduction of the gas-liquid phase separation as the anisotropy of the interaction potential becomes more pronounced; in particular, the RISM theory provides reasonable predictions for all coexistence curves, bar the strong anisotropy regime, whereas OPT performs generally less well. Both theories predict a linear dependence of the critical temperature on the interaction strength, reproducing in this way the mean-field behavior observed in simulations; the critical density—that drastically drops as the anisotropy increases—turns to be less accurate. Our results appear as a robust benchmark for further theoretical studies, in support to the simulation approach, of self-assembly in model colloidal systems.
Authors:
; ;  [1] ;  [2] ;  [3] ;  [4]
  1. Dipartimento di Fisica e di Scienze della Terra, Università degli Studi di Messina, Viale F. Stagno d’Alcontres 31, 98166 Messina (Italy)
  2. C/Clavel 101, Mairena del Aljarafe, 41927 Seville (Spain)
  3. Dipartimento di Fisica and CNR-ISC, Università di Roma “Sapienza,” Piazzale Aldo Moro 2, 00185 Roma (Italy)
  4. Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca’ Foscari Venezia, Calle Larga S.Marta DD2137, Venezia I-30123 (Italy)
Publication Date:
OSTI Identifier:
22415979
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 22; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANISOTROPY; BENCHMARKS; COLLOIDS; COMPARATIVE EVALUATIONS; CRITICAL TEMPERATURE; DIAGRAMS; FREE ENERGY; LIQUIDS; MEAN-FIELD THEORY; PERTURBATION THEORY; POTENTIALS; REDUCTION; SPHERES