Abstract: We have investigated the transitions between disordered phases in supercooled liquid silicon using computer simulations. The thermodynamic properties were directly obtained from the free energy, which was computed using the recently proposed reversible scaling method. The calculated free energies of the crystalline and liquid phases of silicon at zero pressure, obtained using the environment dependent interatomic potential, are in excellent agreement with the available experimental data. The results show that, at zero pressure, a weak first-order liquid–liquid transition occurs at 1135 K and a continuous liquid–amorphous transition takes place at 843 K. These results are consistent with the existence of a second critical point for the liquid–liquid transition at a negative pressure Ver menos