Anomalous properties in the potential energy landscape of a monatomic liquid across the liquid-gas and liquid-liquid phase transitions.

As a liquid approaches the gas state, the properties of the potential energy landscape (PEL) sampled by the system become anomalous. Specifically, (i) the mechanically stable local minima of the PEL [inherent structures (IS)] can exhibit cavitation above the so-called Sastry volume, v, before the liquid enters the gas phase. In addition, (ii) the pressure of the liquid at the sampled IS [i.e., the PEL equation of state, P(v)] develops a spinodal-like minimum at v. We perform molecular dynamics simulations of a monatomic water-like liquid and verify that points (i) and (ii) hold at high temperatures. However, at low temperatures, cavitation in the liquid and the corresponding IS occurs simultaneously and a Sastry volume cannot be defined. Remarkably, at intermediate/high temperatures, the IS of the liquid can exhibit crystallization, i.e., the liquid regularly visits the regions of the PEL that belong to the crystal state. The model liquid considered also exhibits a liquid-liquid phase transition (LLPT) between a low-density and a high-density liquid (LDL and HDL). By studying the behavior of P(v) during the LLPT, we identify a Sastry volume for both LDL and HDL. The HDL Sastry volume marks the onset above which IS are heterogeneous (composed of LDL and HDL particles), analogous to points (i) and (ii) above. However, the relationship between the LDL Sastry volume and the onset of heterogeneous IS is less evident. We conclude by presenting a thermodynamic argument that can explain the behavior of the PEL equation of state P(v) across both the liquid-gas phase transition and LLPT.