Underpinnings behind the magnetic order-to-disorder transition and property anomaly of disproportionated insulating samarium nickelate

Perovskite nickelates (RNiO ₃ ), as benchmark materials for exploring underlying physics of phase transitions in strong correlated systems, are well-known for their rich structural characteristics and physicochemical properties. Understanding phase transition from the spin-ordered antiferromagnetic (AFM) state to the spin-disordered paramagnetic (PM) state of RNiO ₃ requires accurate models at finite temperatures. Here, we investigate the underpinning physics behind the property anomaly and AFM-to-PM transition in samarium nickelate (SmNiO ₃ ) using a thermodynamic zentropy approach, which depicts the temperature-dependent total entropy for a system of interest via a nested formula through integration of quantum mechanics and statistical mechanics. The SmNiO ₃ displays the ground-state of AFM insulator as well as the PM metal and PM insulator at elevated temperatures. It turns out that the magnetic configurational entropy induced by competition among different spatially fluctuating polymorphous spin configurations, contributes to the specific-heat anomaly and the phase transition of SmNiO ₃ from AFM to PM state. The predicted Néel temperature of 241±25 K for SmNiO ₃ is in satisfactory agreement with the experimental value. Unlike empirical interpretations in literature, the present work indicates that the magnetic order-to-disorder transition in SmNiO ₃ is associated with the magnetic configurational entropy due to thermal mixture of multiple spin configurations at elevated temperatures, which can be quantitively captured by the first-principles based thermodynamic zentropy approach.