Abstract
The temperature-induced high-spin(HS)-low-spin(LS) transition of the 3d4-3d7 transition-metal ions in crystals (oxides and sulphides) are investigated on a semiquantitative basis by taking into account the elastic interaction between HS (or LS) clusters produced in a LS (or HS) crystal. The critical temperature at which the discontinuous phase transition takes place is evaluated as a function of the ligand-field strength Delta in units of spin-pairing energy Pi . It is shown that the 'crossover range' where this critical temperature exists is restricted to a finite range of Delta / Pi around the crossover point. The crossover ranges are evaluated for the crystals MO, MS2, M2O3, and LaMO3 where M represents transition-metal ions. The temperature variation of the equilibrium concentrations of HS and LS clusters in LS and HS crystals, respectively, is calculated for several values of Delta / Pi in perovskite LaMO3 crystals. It is pointed out that two discontinuous transitions from HS to LS and LS to HS with decreasing temperature may be expected in the d6 and the d7 systems.
Published Version
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