Monte Carlo simulation of thermodynamic systems with cluster formation under different boundary conditions Original Research Article

Thethermodynamic state function free energy F(T,V,N) as function of the cluster distribution N and the thermodynamic parameters (temperature T and volume V) is calculated in the canonical ensemble. With the help of the Legendre transformation we get all other state functions for different boundary conditions. Monte Carlo simulations with 15000 particles starting from metastable homogeneous initial conditions are made for water and methanol. The Bethe-Weizsäcker ansatz and the Padé approximation are used for the binding energy of clusters. A first-order phase transition is observed under appropriate conditions.