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Equilibrium phase behavior of polydisperse hard spheres
1Department of Mathematics, King's College London, London WC2R 2LS, United Kingdom. moreno.fasolo@kcl.ac.uk
Physical Review Letters
|August 26, 2003
Summary
This study reveals that hard spheres with size variation exhibit complex phase behavior. A terminal polydispersity for solid phases is identified around 7%, with potential for multiple solid-fluid coexisting phases.
Area of Science:
- Statistical Mechanics
- Materials Science
- Thermodynamics
Background:
- Understanding the phase behavior of polydisperse systems is crucial in materials science.
- Previous simplified models for hard spheres with size polydispersity have limitations.
Purpose of the Study:
- To accurately calculate the phase behavior of hard spheres with size polydispersity.
- To investigate the complete phase diagram, including fractionation effects.
Main Methods:
- Utilized accurate free energy calculations for fluid and solid phases.
- Employed the moment free energy method to determine cloud and shadow curves.
- Computed the complete phase diagram, accounting for fractionation.
Main Results:
- No point of equal concentration between fluid and solid phases was found.
- Reentrant melting at higher densities was not observed.
- A terminal polydispersity for solid phases was determined to be approximately 7%.
- Fractionation into multiple solid phases and coexistence with a fluid phase is possible at higher polydispersities.
Conclusions:
- The phase behavior of polydisperse hard spheres is more complex than previously modeled.
- The moment free energy method provides accurate predictions for these systems.
- The findings have implications for the design and understanding of materials with size variation.