Tethered-particle model : the calculation of free energies for hard-sphere systems

Moir, Craig and Lue, Leo and Bannerman, Marcus N. (2021) Tethered-particle model : the calculation of free energies for hard-sphere systems. Journal of Chemical Physics, 155 (6). 064504. ISSN 0021-9606 (https://doi.org/10.1063/5.0058892)

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Two methods for computing the entropy of hard-sphere systems using a spherical tether model are explored, which allow the efficient use of event-driven molecular-dynamics simulations. An intuitive derivation is given, which relates the rate of particle collisions, either between two particles or between a particle and its respective tether, to an associated hypersurface area, which bounds the system's accessible configurational phase space. Integrating the particle-particle collision rates with respect to the sphere diameter (or, equivalently, density) or the particle-tether collision rates with respect to the tether length then directly determines the volume of accessible phase space and, therefore, the system entropy. The approach is general and can be used for any system composed of particles interacting with discrete potentials in fluid, solid, or glassy states. The entropies calculated for the liquid and crystalline hard-sphere states using these methods are found to agree closely with the current best estimates in the literature, demonstrating the accuracy of the approach.