Observation of three sites for vanadyl in a biomineral, zinc sodium phosphate hexahydrate: an EPR investigation

Single crystal EPR study has been carried at room temperature for VO(II) doped zinc sodium phosphate hexahydrate. Single crystal rotations in each of the three mutually orthogonal crystallographic planes namely bc, ac, and ab indicate three chemically inequivalent sites, with intensity ratios of 25:13:1. The spin Hamiltonian parameters obtained for the two intense sites are: Site I: g_xx=1.983, g_yy=1.985, g_zz=1.933; A_xx=7.39 mT, A_yy=7.15 mT, A_zz=19.03 mT; Site. II: g_xx=1.985, g_yy=1.985, g_zz=1.937; A_xx=7.36 mT, A_yy=7.25 mT, A_zz=18.67 mT. The two VO bond directions in the two sites are approximately at right angles to each other. The powder spectrum clearly indicates two chemically inequivalent sites, confirming the single crystal analysis. Admixture coefficients, Fermi contact, and dipolar interaction terms have also been evaluated.