Monte Carlo calculations on the Beta-Delta phase transition in nitrogen with a generalized free energy method

Monte Carlo simulations that utilize an (N, P, T) ensemble with periodic deformable boundary conditions cannot describe phase transitions properly when a large potential barrier is involved. An alternative method is to calculate the Gibbs free energy difference between phases; the transition occurs when the difference is equal to zero. The Gibbs free-energy difference can be calculated using a generalized free-energy method. This method is used to determine theβ-δ phase transition of solid nitrogen at room temperature. The Gibbs free-energy difference between theβ and theδ phase was obtained at 4.0 GPa. The difference at other pressures could be determined with the equation of state. The transition pressure was found at about 6.2 GPa, 1.3 GPa above the experimental pressure.