 
 
 ¶Perovskites such as BaTiO3 with formula ABX3 are a common type of mineral structure, and include many
interesting materials such as ferro-electrics and superconductors. The large blue A-cations 
and red X-anions, often oxygen, are cubic close packed, with the smaller B-cations 
occupying the octahedral holes between the X-anions. 
This is typical of a structure that is best understood by drawing the 
¶BX3 octahedra enclosing the 
B-cation.
 
¶Perovskites such as BaTiO3 with formula ABX3 are a common type of mineral structure, and include many
interesting materials such as ferro-electrics and superconductors. The large blue A-cations 
and red X-anions, often oxygen, are cubic close packed, with the smaller B-cations 
occupying the octahedral holes between the X-anions. 
This is typical of a structure that is best understood by drawing the 
¶BX3 octahedra enclosing the 
B-cation.  
 The stability of the structure depends on the 
relative ionic radii: if the cations are too small for close packing with the oxygens,
they can be displaced slightly.  Since these ions carry 
electrical charges, such displacements can result in a net electric dipole moment
(opposite charges seperated by a small distance).  The material is said to be
a ferro-electric by analogy with a ferro-magnet which contains magnetic dipoles.
 
The stability of the structure depends on the 
relative ionic radii: if the cations are too small for close packing with the oxygens,
they can be displaced slightly.  Since these ions carry 
electrical charges, such displacements can result in a net electric dipole moment
(opposite charges seperated by a small distance).  The material is said to be
a ferro-electric by analogy with a ferro-magnet which contains magnetic dipoles.
 At high temperature, the small green B-cations can "rattle around" in the larger holes between oxygen,
maintaining cubic symmetry.  The 
¶static displacement only occurs when the structure 
is cooled below a certain transition temperature.  We have illustrated a 
dispacement along the z-axis, resulting in tetragonal symmetry (z remains a 
4-fold symmetry axis), but at still lower temperatures the symmetry can be
lowered further by additional displacements along the x- and y-axes. We have a 
¶dynamic 3D-drawing of this ferro-electric transition.
 
At high temperature, the small green B-cations can "rattle around" in the larger holes between oxygen,
maintaining cubic symmetry.  The 
¶static displacement only occurs when the structure 
is cooled below a certain transition temperature.  We have illustrated a 
dispacement along the z-axis, resulting in tetragonal symmetry (z remains a 
4-fold symmetry axis), but at still lower temperatures the symmetry can be
lowered further by additional displacements along the x- and y-axes. We have a 
¶dynamic 3D-drawing of this ferro-electric transition.
 An alternative type of structural transition, called anti-ferroelectric, 
is also common in perovskites.  If the A-cation is too large for close packing,
the X-cations can be displaced instead. But since the BX6 octahedrae are
relatively rigid units connected at their apexes, they twist together as in
¶NaNbO3.  Again, we have a 
¶dynamic 3D-drawing of this anti-ferroelectric transition.  There is no net dipole 
moment in such 
anti-ferroelectric structures.  Again, as the temperature is lowered, a
succession of transitions can occur, with the octahedrae twisting around
different axes.
 
An alternative type of structural transition, called anti-ferroelectric, 
is also common in perovskites.  If the A-cation is too large for close packing,
the X-cations can be displaced instead. But since the BX6 octahedrae are
relatively rigid units connected at their apexes, they twist together as in
¶NaNbO3.  Again, we have a 
¶dynamic 3D-drawing of this anti-ferroelectric transition.  There is no net dipole 
moment in such 
anti-ferroelectric structures.  Again, as the temperature is lowered, a
succession of transitions can occur, with the octahedrae twisting around
different axes.
Ferro-electric and other di-electric materials have important applications 
as sensors, since a physical change in the dimensions of the material is
accompanied by an electric field.  But so far we have concentrated on 
bonding between electrically charged ions. What about the strong 
covalent bonding between atoms that is 
responsible for the strength of diamonds ?