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Phase behavior of parallel hard cylinders.

José A Capitán1, Yuri Martínez-Ratón, José A Cuesta

  • 1Grupo Interdisciplinar de Sistemas Complejos, Departamento de Matemáticas, Escuela Politécnica Superior, Universidad Carlos III de Madrid, Avenida de la Universidad 30, E-28911 Leganés, Madrid, Spain. jcapitan@math.uc3m.es

The Journal of Chemical Physics
|May 27, 2008
PubMed
Summary

This study validates a new density functional for hard cylinders by calculating their phase diagram. The functional accurately predicts liquid-crystalline and crystalline phases, showing good agreement with simulations.

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Area of Science:

  • Statistical Mechanics
  • Materials Science
  • Computational Physics

Background:

  • Fundamental measure density functionals are crucial for predicting phase behavior in soft matter systems.
  • Understanding the liquid-crystalline and crystalline phases of hard cylinders is essential for materials design.

Purpose of the Study:

  • To assess the performance of a novel fundamental measure density functional for hard cylinders.
  • To calculate and analyze the phase diagram, including nematic, smectic, columnar, and crystalline phases.

Main Methods:

  • Utilized a Gaussian parametrization of the density profile for numerical minimization of the density functional.
  • Determined bifurcation points for phase transitions using the analytic structure factor of the uniform fluid.
  • Compared the equation of state derived from functional minimization with Monte Carlo simulations.

Main Results:

  • The density functional demonstrated excellent agreement with Monte Carlo simulations, particularly for inhomogeneous phases.
  • The columnar phase was found to be metastable, with free energy close to stable smectic or crystal phases.
  • A minor deviation was observed in the nematic-smectic transition, consistent with limitations of current density functionals.

Conclusions:

  • The proposed fundamental measure density functional is highly accurate for predicting the phase behavior of hard cylinders.
  • The findings explain the observed stability window of the columnar phase in simulations.
  • Further refinement of density functionals is needed to improve the description of uniform phase transitions.