Abstract
X-band electron paramagnetic resonance (EPR) studies of VO 2+ ions have been carried out in a cadmium oxalate trihydrate single crystal. The EPR spectra, recorded at 295, 80, 42, 19 and 4.2 K, are indicative of a single VO 2+ site in the unit cell. Each vanadyl hyperfine line is characterized by an anisotropic triplet superhyperfine (SHF) splitting, with the intensity ratios 1:2:1; maximum separation of the SHF splitting is observed when the orientation of the external magnetic field is along the Cd-H 2O(II) direction. The principal values, and the direction cosines of the principal axes of the g̃ 2 and à 2 tensors are evaluated from a simultaneous fitting of the EPR line positions, observed for several orientations of the external magnetic field, using a rigorous least-squares-fitting program, suitable for electron-nuclear spin-coupled systems. An impurity model of the vanadyl ion, substituting for the divalent cadmium ion, is proposed. The orientation of the V 4+-O 2- bond has been estimated to be close to the Cd-H 2O(I) direction. The SHF structure is explained to be due to the interaction of the unpaired electron of the VO 2+ ion with the two protons of its nearest-neighbor water molecule H 2O(II); the principal values and the orientations of the principal axes of the SHF interaction tensor have been estimated.
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