Thermodynamic anomalies in silicon and the relationship to the phase diagram

Abstract

Abstract The evolution of thermodynamic anomalies are investigated in the pressure–temperature (pT) plane for silicon using the well-established Stillinger–Weber potential. Anomalies are observed in the density, compressibility and heat capacity. The relationships between them and with the liquid stability limit are investigated and related to the known thermodynamic constraints. The investigations are extended into the deeply supercooled regime using replica exchange techniques. Thermodynamic arguments are presented to justify the extension to low temperature, although a region of phase space is found to remain inaccessible due to unsuppressible crystallisation. The locus corresponding to the temperature of minimum compressibility is shown to display a characteristic ‘S’-shape in the pT projection which appears correlated with the underlying crystalline phase diagram. The progression of the anomalies is compared to the known underlying phase diagrams for both the crystal/liquid and amorphous/liquid states. The locations of the anomalies are also compared to those obtained from previous simulation work and (limited) experimental observations.