Wednesday, February 04, 2004

Solid vs. Liquid, The Free Energy Battle


Determining the free energy difference between the solid and liquid states is essential for accurately mapping the phase diagram of a substance. Typically, one determines the free energies of the solid and liquid states through separate thermodynamic integrations, where each integration has one end point connected to a state with an analytically known free energy. In the solid state, the Einstein crystal (springs attaching particles to lattice sites) is often used as a starting point. In the liquid state, the low density gas can be used as an end point. Other more complicated scalings of the potential are also possible for the integration path.


A direct integration path between the solid and liquid states would be useful.
Gregory Grochola has published one such path in "Constrained fluid lambda-integration: Constructing a reversible thermodynamic path between the solid and liquid state"(JCP 120, 2122).


The basic path is to start with the liquid state and turn off the intermolecular potential. Then turn on a potential constraining particles to lattice sites (He used a Gaussian potential). The last step is to turn off the lattice potential while turning the intermolecular potential back on.


He mentions at the end that this method is not very computationally efficient. I would expect using Bennett's method for free energy differences would cut down on the number of intermediate states needed.


Questions


  1. Compare and contrast this path with the phase switching Monte Carlo technique (there's a reference in the article)
  2. Thermodynamic integration requires there be no phase transitions on the path. Is it immediately obvious that this path has no transitions? Under what conditions, if any, would a phase transition occur on the path?

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