Coupling and decoupling of spin crossover and ferroelastic distortion: Unsymmetric hysteresis loop, phase diagram, and sequence of phases
Résumé
Spin-transition materials can exhibit thermal hysteresis due to cooperative elastic interactions in between active molecular sites. It results from the coupling of the nonsymmetry-breaking high spin fraction order parameter to the lattice volume strain. However, a symmetry-breaking order parameter responsible for crystallographic phase transition, like a ferroelastic distortion, can also couple to the volume strain. Here, we use the Landau theory to study the elastic coupling between a spin-crossover instability and a discontinuous ferroelastic distortion and the different phase transition lines. Below the triple point, the first-order line involves simultaneous ferroelastic distortion and spin transition. Above, the purely first-order ferroelastic distortion and the spin crossover occur sequentially. Our model, related to the coupling and decoupling of the ferroelastic phase transition and spin crossover, explains exotic behaviors reported experimentally in the literature for diverse spin-crossover systems, plastic crystals, or Prussian blue analogues. The unsymmetric hysteresis loops and the stepwise evolution of the spin conversion or volume strain under pressure result from different sequences of phase transitions. The model shows that the ferroelastic phase transition is the driving force of the cooperative spin transition hysteresis in this case. © 2021 American Physical Society.