Investigations of g Factors and Local Structures for Cu(en)boldGroups in/bold Cu(en)(3)SO4 and Cu(en)(3)Cu(CN)(3) Polycrystalline Powders

摘要

From the perturbation formulas for g factors for an orthorhombically compressed octahedral 3d(9) group, g factors, and local structures for the [Cu(en)(3)](2+) groups in Cu(en)(3)SO4 and Cu(en)(3)Cu(CN)(3) powders are theoretically investigated. The local structure of Cu2+ in Cu(en)(3)Cu(CN)(3) is evaluated by analyzing the experimental g factors and found to exhibit moderate axial compression Z (approximate to 0.018 angstrom) and planar bond length variation R (approximate to 0.015 angstrom) related to an ideal octahedron due to the Jahn-Teller effect. The larger experimental axial anisotropy g (= (g(x) + g(y))/2 - g(z)) of Cu(en)(3)SO4 than Cu(en)(3)Cu(CN)(3) is mainly ascribed to the larger Z (approximate to 0.053 angstrom) in the former. The calculated g factors for both systems show reasonable agreement with experiment by including the charge transfer (CT) contributions to g(z), which have the same sign and much larger magnitude compared to the conventional crystal-field ones and should be included.