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

Academic Article
Publication Date:
2015
abstract:
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.
Iris type:
01.01 Articolo in rivista
Keywords:
Free energy; Thermodynamic properties; Colloidal systems; Mean field theory Perturbation theory
List of contributors:
Sciortino, Francesco
Handle:
https://iris.cnr.it/handle/20.500.14243/292414
Published in:
THE JOURNAL OF CHEMICAL PHYSICS
Journal
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URL

http://scitation.aip.org/content/aip/journal/jcp/142/22/10.1063/1.4922163
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