Theoretical studies of the spin Hamiltonian parameters for the two tetragonal Cu centers in the calcined catalysts CuO–ZnO

The spin Hamiltonian parameters for the two Cu centers A1 and A2 in the calcined catalysts CuO–ZnO are theoretically investigated using the high order perturbation formulas of these parameters for a 3d ion in tetragonally elongated octahedra. In the above formulas, the tetragonal field parameters Ds and Dt are determined from the superposition model, by considering the relative axial elongation of the oxygen octahedron around the Cu due to the Jahn-Teller effect. Based on the calculations, the relative elongation ratios of about 5% and 3% are obtained for the tetragonal Cu centers A1 and A2, respectively. The theoretical spin Hamiltonian parameters are in good agreement with the observed values for both systems. The larger axial elongation in center A1 is ascribed to the more significant low symmetrical (tetragonal) distortion of the Jahn-Teller effect. The local structures characterized by the above axial elongations are discussed.