The Uhlenbeck–Ford model in two dimensions: Reference system for fluid-phase free-energy calculations

We investigate the Uhlenbeck–Ford (UF) model as a reference system for free-energy calculations in two-dimensional (2D) fluids. The 2D virial coefficients are computed exactly up to the tenth order and combined with molecular simulation data to construct highly accurate numerical representations of the equation of state and the excess Helmholtz free energy. We then determine the phase diagram of the model in order to establish the thermodynamic stability limits of the fluid phase and thereby identify the range of applicability of the UF model as a fluid reference system. In the course of this analysis, we identify the solid, hexatic, and fluid phases and show that the fluid remains the only thermodynamically stable phase, independent of density, for scaling parameters up to p ≲ 70. Finally, we demonstrate the practical applicability of the 2D UF model as a reference system through thermodynamic integration calculations of the free energy of a two-dimensional Lennard-Jones fluid.