The
ground state of Fe2+ (S = 2) in
α- and β-FeMoO4 is investigated by experiments
including X-ray diffraction, Raman scattering, and 57Fe–Mössbauer
spectroscopy below 300 K and evaluated by theoretical modeling. Both
modifications crystallize in the space group C2/m with the same set of Wyckoff positions. The structural
feature of α- and β-FeMoO4 is a tetramer of
the so-called butterfly motif. Two iron-sites (Fe2) form an antiferromagnetically
coupled dimer whereas two Fe1 establish an antiferromagnetic intertetramer
coupling. The effective magnetic exchange of the two magnetic sublattices
is based on dominating Dzyaloshinskii–Moriya interaction due
to the rare situation of canceling Heisenberg exchange interactions.
According to our investigations, the ground states of the two polymorphs
differ in terms of their Fe-site specific electric field gradients V
ii
. Contrary to the α-phase,
a degenerate set of V
zz
and V
yy
for both iron
sites in β-FeMoO4 is extracted from density functional
theory calculations. In the vicinity of the phase transition (β
→ α), the degeneracy of the β-phase is lifted.
Correspondingly, we observe a softening of the ν(Mo–O)
phonon modes. Detailed Mössbauer spectra confirm the crosslike
90° antiferromagnetic structure for both modifications and solve
the origin of the longstanding issue of disparate quadrupole splittings
in α- and β-FeMoO4.
Electronic spectra of 3d(n) transition ions in an octahedral ligand surrounding have been studied using the modified crystal field approach (MCFA), which includes a relativistic spin-orbital interaction. A new variable parameter, the effective nuclear charge Z(eff) of a metal ion that allows accounting implicitly the covalence degree of a metal-ligand bond, has been introduced. Energy diagrams similar to the Tanabe-Sugano ones have been calculated. To study the spin state evolution of the metal ion in an arbitrary distorted octahedral complex, a spin state diagram approach has been proposed. The intermediate-spin (IS) state problem for 3d(4), 3d(5), and 3d(6) metal ions has been considered and conditions for the IS state realization have been formulated. The regions of the mixed high-, intermediate-, and low-spin states have been found. The possibility of coexistence of the different spin states of 3d ions in the octahedral complexes has been considered using crystallography data for the YBaCo(2)O(5.5) layered cobaltite.
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