Paper detail

The Rise and Fall of Anomalies in Tetrahedral Liquids

The thermodynamic liquid-state anomalies and associated structural changes of the Stillinger-Weber family of liquids are mapped out as a function of the degree of tetrahedrality of the interaction potential, focusing in particular on tetrahedrality values suitable for modeling C, H2O, Si, Ge and Sn. We show that the density anomaly, associated with a rise in molar volume on isobaric cooling, emerges at intermediate tetrahedralities (e.g. Ge, Si and H2O) but is absent in the low (e.g. Sn) and high (e.g. C) tetrahedrality liquids. The rise in entropy on isothermal compression associated with the density anomaly is related to the structural changes in the liquid using the pair correlation entropy. An anomalous increase in the heat capacity on isobaric cooling exists at high tetrahedralities but is absent at low tetrahedralities (e.g. Sn). Structurally, this heat capacity anomaly originates in a sharp rise in the fraction of four-coordinated particles and local tetrahedral order in the liquid as its structure approaches that of the tetrahedral crystal.