Simulating the phosphorus fluid-liquid phase transition up to the critical point

We report a Car-Parrinello molecular dynamics study of the temperature dependence of the fluid-liquid phase transition in phosphorous, involving the transformation of a molecular fluid phase into a network-like phase. We employed density-functional theory (DFT) with a gradient-corrected functional (B-LYP) to describe the electronic structure and interatomic interactions and performed simulations in a constant pressure ensemble. We spanned a temperature interval ranging from 2500 to 3500 K. With increasing temperature, we found that the structural conversion from the molecular P-4 fluid into the network liquid occurs at decreasing pressures, consistent with experimental observations. At lower temperatures the transition is characterized by a sudden increase of density in the sample. The magnitude of the density change decreases with increasing temperature and vanishes at 3500 K. In the temperature range 3100-3500 K we found signals of near-and super-criticality. We identified local structural changes that serve as seeds triggering the overall structural transition.