Physical Properties and Symmetry

(elementary introduction)

Piezoelectricity
The piezoelectric effect is understood as the linear electromechanical interaction between the mechanical and the electrical state in crystalline materials with no inversion symmetry. The piezoelectric effect is a reversible process in that materials exhibiting the direct piezoelectric effect (the internal generation of electrical charge resulting from an applied mechanical force) also exhibit the reverse piezoelectric effect (the internal generation of a mechanical force resulting from an applied electrical field). -- Wikipedia

Properties like piezoelectricity are only possible in crystalline materials that have no center of symmetry. Otherwise a charge separation cannot be developed. So we must look to the symmetry of the atoms in the unit cell to determine if an otherwise macroscopic property exists. To understand which crystal symmetries can support such an effect, we need to look at the point group of the space group. We are interested in the point group of the space group because translational symmetry at the unit cell level does not affect the existence of a property.

Obtaining the the point group of a given space group is relatively easy. We simply remove the space group centering operation (P, I, F, A, B, C) and then convert any symmetry elements containing translations (screw axes and glides) to their nontranslational equivalents (rotations and mirrors).

Pbca P42nm

------------------> ------------------>

mmm 4mm

Of the 32 crystallographic point groups, we can eliminate the 11 point groups containing an inversions center (centosymmetric). This then leaves 21 possible point groups that can support piezoelectricity. Eliminated:

1 2 m mmm 4 m 4 m mm 3 3m 6 m 6 m mm m3 m3m

One other point group can be eliminated because of its symmetry elements. This is a cubic point group whose symmetry elements prevent charge separation. It is 432.

This leaves a total 20 point groups that can sustain a property like piezoelectricity these groups can be divided into two classes, one of which are the polar point groups.

Polar Point Groups

Point groups having a unique axis that is not repeated in any direction.

1 2 3 4 6 m mm2 3m 4mm 6mm

The polar point groups can support spontaneous polarization of charge without any mechanical stress due to a nonvanishing electric dipole moment associated with the unit cell. Materials in these systems also support pyroelectricity (temperature driven charge distribution).

The remaining 10 point groups also support the piezoelectric effect but do not support a spontaneous polarization. Here the stress applied to the material can be thought of as transforming the point group from a non-polar one to a polar point group.

222 6

422 42m 32

6 m2 622 43m 23

Phase Changes Can Affect Physical Properties

m3m

4mm

Birefrengence

Light waves passing through a single crystal are affected differently if they are aligned with a symmetry axis than if they are aligned perpendicular to that direction. With initially unpolarized light, the waves perpendicular to the symmetry axis will be refracted (bent) differently from those aligned with the axis. This effect is known as birefringence. If light is passed through a crystal along a symmetry axis, it only sees one environment and the birefringence disappears. The effect is different for different crystal classes. So, symmetry plays an important role in determining refractive index properties.

Cubic
Because of the multiple 3-fold axes, cubic crystals do not have a unique axis. The refractive index is isotropic and birefringence cannot occur.

Uniaxial
Tetragonal Hexagonal Trigonal

Principal symmetry axis (3, 4, 6) is the Optic Axis Light entering off the Optic Axis sees two refractive indexes from: Light vibrating parallel to optic axis

Light vibrating perpendicular to optic axis

Birefringence is observed. Light entering parallel to the Optic axis sees one refractive index Birefringence does not occur. Isotropic

Orthorhombic

Monoclinic

Triclinic

Crystals in these systems have three refractive indexes and two principal optic axes along which light waves pass in an isotropic manner. These materials are said to be bi-axial Examine an elliptical solid to see why there are two principal

axes.

Physical Property Dependencies

J.F. Nye, "Physical Properties of Crystals" (1957)

Each property in the previous diagram is given a dimension. 0 represents a scalar, 1 a vector and in general n represents a n rank tensor. Look at pyroelectricity for example. The polarization P (a vector) is produced by a temperature T (scalar). The relationship is thus:

P pT
The pyroelectric effect, p, must also be a vector in this equation. Symmetry helps determine the possible values in p.

Triclinic
No symmetry restrictions: p = [ p1 p2 p3 ]

Monoclinic
Class 2: p = [ 0 p2 0 ] P vector along 2-fold Class m: p = [ p1 0 p3 ] P vector in x-z plane

Orthorhombic
Class mm2: p = [ 0 0 p3 ] P vector along 2-fold
Class m: p = [ 0 0 0 ] No effect observed

Tetragonal Hexagonal Trigonal

Polar classes: p = [ 0 0 p3 ] Other classes: p = [ 0 0 0 ]

Cubic
p = [ 0 0 0 ] No effect observed