Electron paramagnetic resonance study of Cu(II) in the Cu(II) doped (NH4)2[Zn(NH3)2(CrO4)2] and (NH4)2[Cd(NH3)2(CrO4)2]: Orientational disorder of NH3 and dynamically induced structural change

Abstract

Electron paramagnetic resonance (EPR) spectra recorded at X band on Cu(II) in the Cu(II) doped single crystals of (NH4)2[Zn(NH3)2(CrO4)2] and (NH4)2[Cd(NH3)2(CrO4)2] showed an unusual temperature dependence in the temperature range between 4.2 and 370 K. This unusual temperature dependence is attributed to the dynamics of NH3 molecules. It is concluded that NH3 undergoes an order–disorder transition. This transition occurs at 282±2 K (T*) for (NH4)2[Zn(NH3)2(CrO4)2] and at 300±5 K for (NH4)2[Cd(NH3)2(CrO4)2]. For temperatures above T* the EPR spectra are found independent of temperature. This observation indicates that the NH3 molecules behave as free rotors rotating about their threefold symmetry axis. As the temperature is lowered, the free rotation gradually becomes hindered which leads at T* to site doubling in the EPR spectra. The hindered rotation simultaneously induces a structural change at T* reducing the local symmetry at the Cu(II) site from C2/m to approximately Cs. In the temperature range between T* and about 80 K, the EPR spectra with the magnetic field perpendicular to the threefold axis of NH3 are temperature dependent, but those with the magnetic field parallel to the threefold axis remain unchanged. This behavior is qualitatively interpreted as being due to the torsional oscillation of NH3. At temperatures lower than 80 K, the NH3 molecules exhibit the torsional oscillation of the lowest state and accordingly, all the EPR spectra become temperature independent.