The temperature dependence of the EPR spectrum of Cu2+ in ZnTiF6⋅6H2O between 4 and 160 K

Abstract

The EPR spectrum of Cu2+ in the low temperature monoclinic phase of ZnTiF6⋅6H2O was studied at 9.24 GHz between 4 and 160 K. Assuming the Jahn–Teller spectra to have axial symmetry, g∥ was found to vary from 2.472±0.004 at 4 K to 2.331±0.004 at 158 K, while g⊥ varied from 2.097±0.004 to 2.173±0.004 over this range. From the temperature variations of the g values, the lowering of the energy Δ of one potential well associated with the Jahn–Teller distortion compared to the other two was found to be approximately 143 cm−1. It is shown that an apparent decrease in Δ with increasing temperature above 100 K could be due to the presence of an excited vibronic state about 170 cm−1 above the ground state. The variation of ‖A∥‖ from (107±1)×10−4 cm−1 at 4 K to (53±3)×10−4 cm−1 at 158 K agreed with predictions based on the temperature variation of the g tensor.