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3) Ligand-Fleld Stabilization Energies: Applicable whenever there are transition metal ions
and is discussed below.
The structures of spinels are affected by the relative LFSE values of metal ions. The ion with
more LFSE value in octahedral geometry when compared to the LFSE in tetrahedral
geometry tends to occupy octahedral sites.
The difference between the LFSE values in octahedral and tetrahedral geometries is referred to as
Octahedral Site Stabilization Energy (OSSE).
If the BIII ion has more CFSE gain in octahedral site than that of AII ion, a normal
spinel is expected.
Whereas an inverse spinel is formed whenever the divalent A II ion has comparatively
more CFSE gain in octahedral geometry than the trivalent B III ion.
BIII
Structure
Non transition
Spinel structure
metal
d0 or d5 or d10
transition metal
A transition metal
with
Non transition
metal
d1 or d2 or d3 or
or
d or d or d
0
10
d4 or d6 or d7 or d8
Spinel structure
or d9
transition metal
configurations
A transition metal
Non transition
with
metal
d1 or d2 or d3 or
d4 or d6 or d7 or d8
or d9
configurations
or
transition meta
Inverse spinel
with
d or d5 or d10
0
configurations
Transition metal
Transition metal
value
value
Inverse spinel
lattice energy. This leads to almost complete randomization of all the cations on all the available sites.
Its formula can be written as (Al0.75Ni0.25)tet [Ni0.75Al1.25]octaO4.