材料期刊网

The complete high-order perturbation formulas of EPR parameters (g-shifts Delta g(parallel to),Delta g(perpendicular to) and zero-field splitting D), including not only the crystal-field (CF) mechanism, but also the charge-transfer (CT) mechanism (which is neglected in crystal-field theory), are established by a cluster approach for 3d(2) ions in trigonal symmetry. From these formulas, the EPR parameters of Y2SiO4:Cr4+, Ba-3(VO4)(2):Mn5+ and K2CrO4:Fe6+ are calculated. The results are in reasonable agreement with the observed values. It is found that the relative importance of CT mechanism increases with increasing atomic number of 3d(2) ion and so in the studies of EPR parameters for high valence state 3d" ions in crystals, both CF and CT mechanisms should be taken in account. (c) 2005 Elsevier B.V. All rights reserved.