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EPR of electron irradiated K/sub 4/Os/sup II/(CN)/sub 6/ in KCl single crystals

Journal Article · · J. Chem. Phys.; (United States)
OSTI ID:5120087

Electron irradiation of the diamagnetic Os/sup II/(CN)/sub 6//sup 4 -/ ion in a KCl host lattice at 77 /sup 0/K produces three paramagnetic species. Annealing experiments reveal that these species decay into at least four other species. EPR studies indicate that each species can be assigned to a pentacoordinated Os/sup I/(CN)/sub 5/ complex, with 5d/sup 7/ low spin configuration arising from the trapping of an electron in a d/sub z/2 orbital, associated with a charge compensating vacancy located at different lattice sites. The EPR spectra show a strong quadrupolar interaction. The g values, the magnetic hyperfine interaction, and a minimum value for the quadrupolar interaction with the /sup 189/Os nucleus are presented and discussed. Ligand hyperfine structure with four equivalent and one nonequivalent nitrogens is measured and the ligand f/sub s/ and f/sub p/ spin densities are calculated and discussed. The relative contribution of 5d and 6p electrons to the electric field gradient is discussed and compared with Moessbauer spectroscopy results.

Research Organization:
Centro Brasileiro de Pesquisas Fisicas, Av. Wenceslau Braz 71, Rio de Janeiro, Brazil
OSTI ID:
5120087
Journal Information:
J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 68:7; ISSN JCPSA
Country of Publication:
United States
Language:
English