Theoretical investigations of spin‐Hamiltonian parameters for Ru³⁺ ions in rutile (TiO₂) crystal

Abstract

In this paper, we present two diagonalization of energy matrix methods (DEM‐I and DEM‐II) to calculate the spin‐Hamiltonian (SH) parameters of the low‐spin d5 configuration (with the ground state 2T2 and spin S = 1/2) in rhombic symmetry. The x ‐ and y‐axes in which SH parameters are expressed are taken along the bisectors of the angles between metal‐ligand bonds in crystals e.g., rutile‐type crystals. In DEM‐I, the Hamiltonian related to energy matrix within the 2T2 term does not contain the Zeeman interaction and hyperfine interaction, whereas in DEM‐II, it does. Based on the two methods, the SH parameters (g factors gi, hyperfine structure constants 99Ai and 101Ai, where i = x, y, z) of Ru3+ (4d5) ions in TiO2 are calculated. The results from both methods coincide and are also in reasonable agreement with the experimental values. So, both methods are reliable for prediction of SH parameters for the low‐spin d5 ions in crystals. The signs of hyperfine structure constants Ai are also suggested from the calculations. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Studies of the spin-Hamiltonian parameters, d–d transitions and defect structures for two tetragonal Cu2+ centers in Ba2ZnF6:Cu2+ crystal

“…z and P the spin-orbit coupling parameter and dipolar hyperfine structure constant, respectively. A covalence reduction factor N 2 is introduced to represent the covalence [12][13][14][15][16] …”