Th. Yeom et al., EPR STUDY OF LOW-SYMMETRY MN2- SUPERPOSITION MODEL AND CRYSTAL-FIELD ANALYSIS OF THE ZERO-FIELD SPLITTING PARAMETERS( CENTERS IN LINBO3 ), Physica status solidi. b, Basic research, 185(2), 1994, pp. 417-428
X-band EPR spectra of Mn2+:LiNbO3 single crystals at room temperature
are analyzed with a spin-Hamiltonian of C-3 symmetry. Experimental dat
a are interpreted using the superposition model in a twofold way. Firs
tly, the zero-field splitting (ZFS) parameters b(2)(0), b(4)(0), b(3)(
4), and b(4)(-3) are predicted. While the results for b(2)(0) are not
conclusive, those for the major fourth-order ZFS term \upsilon(4)(3)\
= [(b(3)(4))(2) + (b(4)(-3))(2)](1/2) indicate better agreement with e
xperiment, assuming Mn2+ at the Nb site. Secondly, crystal field (CF)
parameters are obtained from the superposition model using two sets of
available structural data. Diagonalization of the CF Hamiltonian with
in the whole 3d5 configuration yields the theoretical ZF splittings. T
he results for Mn2+ at the Nb site agree better with the experimental
data than those for Mn2+ at the Li site. Hence the superposition model
analyses of the observed EPR spectra indicate that the spectra can be
most likely attributed to Mn2+ ions at Nb sites. The ways to reconcil
e this conclusion with the opposite one from the low temperature ENDOR
study are discussed.