Phase transitions of liquid phosphorus: constant-pressure first-principles molecular dynamics simulations

Abstract Liquid–liquid phase transitions of phosphorus were studied by constant-pressure first-principles molecular dynamics simulations. In the compression of a molecular liquid (a low-pressure phase) consisting of the tetrahedral P 4 molecules, a structural phase transition from the molecular to polymeric liquid (a high-pressure phase) was realized. This is consistent with the recent experiment by Katayama et al. [Nature 403 (2000) 170]. It is shown that this transition is characterized by large volume contraction accompanying a breakup of the tetrahedral molecules.