Limit of Superheating and Supercooling in Solid‐Liquid Transitions

The inherent free energy barrier to the first‐order phase transition may give rise to metastable melting and crystallization, i.e., superheating and supercooling. The systematics for the maximum superheating and supercooling at a given heating or cooling rate have been established based on classical nucleation theory and supercooling experiments. Over‐pressurization and over‐depressurization are equivalent to superheating and supercooling. The systematics have been demonstrated to be consistent with molecular dynamics simulations, Landau models and experiments. The applications of the systematics include the interpretation of dynamic experiments and molecular dynamics simulations, and the hysteresis method for determining the equilibrium melting temperature and the solid‐liquid interfacial energy from superheating or supercooling.