QUADRATIC CRYSTAL-FIELD TENSORS AND SPIN-HAMILTONIAN TENSORS OF FE3-TRANSITION TEMPERATURE( IN LI2GE7O15 ABOVE AND BELOW THE PHASE)

Dopant Fe3+ ions in tetrahedral and octahedral positions of Ge4+ in th e crystal Li2Ge7O15 were studied using EPR. Fe3+ substitutes for Ge4with a local charge compensation. The octahedral site and the tetrahed ral sites significantly differ by the value of the invariant sum S(B-4 ) of the B-4 tensor of the spin Hamiltonian of Fe3+. The irreducible t ensor products {V-4 circle times V-4}(4) and {V-4 circle times V-4}(2) of the V-4 tensor of the crystal field calculated using the point-cha rge model for octahedral and tetrahedral complexes provide the predomi nant contribution of the crystal field to the B-4 and B-2 tensors of t he spin Hamiltonian of Fe3+, respectively. A comparison of the fourth- rank tensors B-4 of the spin Hamiltonian and {V-4 circle times V-4}(4) of the crystal field determined at 300 K with those determined at 77 K supports the conclusion that the phase transition is accompanied by combined rotations of the [GeO4] tetrahedra with the [Ge(1)O-6] octahe dron almost unaltered. The spectrum lines are narrow and the variety o f point defects in the vicinity of the paramagnetic impurity ions Fe3, Cr3+ and Cu2+ is not detected. These facts are inconsistent with the statistically distributed model for the Li(2) atom. In specific cases at 300 K, when the wings of the two spectrum lines of the M --> M+1 a nd the M+2 --> M+3 transitions of Fe3+ ions belonging to one system of translationally equivalent positions overlap an extra line appears in the center between these lines. It is suggested that this effect is d ue to the soft phonon mode above the phase transition temperature.