EPR Study of Ammonium Nitrate Doped with Copper(II) Ions

This work is devoted to a study of the structural changes in a single crystal of ammonium nitrate, NH4NO3, doped with copper(II) cations by electron paramagnetic resonance. Ammonium nitrate crystallizes at atmospheric pressure in several polymorphic forms, phase VII → V → IV → III → II → I → melt, with transition temperatures of 103 K, 255 K, 305 K, 357 K, 398 K, and 443 K, respectively. The aim of our work was to study the temperature phase transition V → IV at about 255 K using electron paramagnetic resonance technique. The electron paramagnetic resonance spectra were performed using an X-band spectrometer with microwave frequency of 9.4 GHz and magnetic modulation of 100 kHz in the temperature range of 153–296 K. For a single crystal the angular dependence of the copper(II) electron paramagnetic resonance spectra was measured at 293 K and 168 K. The anisotropic behaviour measured at 293 K points to the existence of one kind of two equivalent copper(II) complexes with inverse g and A tensors. A second pair of equivalent complexes also with inverse g and A tensors was observed. The minimal values of g-factors correspond to the maximum values of A. The angular dependence taken at 168 K shows the existence of two types of non-equivalent copper complexes which differ in comparison with the complexes observed at room temperature. The temperature dependence of the intensities of hyperfine structure lines for all copper(II) complexes observed shows a phase transition V → IV occurring in the temperature range of 237–246 K with a hysteresis. One of the hyperfine structure lines of a copper(II) complex measured at low temperatures shows a superhyperfine structure with line intensities 1:2:3:2:1 originating from the interaction of the copper Cu (I = 3/2) nucleus with two N (I = 1) nuclei of two ammonia, NH3, ligand molecules.