EPR observation of phase transitions in calcium cadmium acetate hexahydrate: Using Mn2+ and Cu2+ ions as probe

Results of temperature dependence of EPR spectra of Mn2+ and Cu2+ ions doped calcium cadmium acetate hexahydrate (CaCd(CH3COO)4•6H2O) have been reported. The investigation has been carried out in the temperature range between room temperature ( 300 K) and liquid nitrogen temperature. A I-order phase transition at 146 ± 0.5 K has been confirmed. In addition a new II-order phase transition at 128 ± 1 K has been detected for the first time. There is evidence of large amplitude hindered rotations of CH3 groups which become frozen at 128 K. The incorporation of Cu2+ and Mn2+ probes at Ca2+ and Cd2+ sites respectively provide evidence that the phase transitions are caused by the molecular rearrangements of the common coordinating acetate groups between Ca2+ and Cd2+ sites. In contradiction to the previous reports of a change of symmetry from tetragonal to orthorhombic below 140 K, the symmetry of the host is concluded to remain tetragonal in all the three observed phases between room temperature and liquid nitrogen temperature.