Nearly-free electron model

In solid-state physics, the nearly-free electron model (or NFE model) is a quantum mechanical
model of physical properties of electrons that can move almost freely through the crystal lattice
of a solid. The model is closely related to the more conceptual Empty Lattice Approximation.
The model enables understanding and calculating the electronic band structure of especially
metals.
Crystal structure
From Wikipedia, the free encyclopedia

In mineralogy and crystallography, crystal structure is a unique arrangement of atoms or

molecules in a crystalline liquid or solid. A crystal structure is composed of a pattern, a set of
atoms arranged in a particular way, and a lattice exhibiting long-range order and symmetry.
Patterns are located upon the points of a lattice, which is an array of points repeating periodically
in three dimensions. The points can be thought of as forming identical tiny boxes, called unit
cells, that fill the space of the lattice. The lengths of the edges of a unit cell and the angles
between them are called the lattice parameters. The symmetry properties of the crystal are
embodied in its space group.
A crystal's structure and symmetry play a role in determining many of its physical properties,
such as cleavage, electronic band structure, and optical transparency.

Insulin crystals.

Contents
[hide]

1 Unit cell
o

1.1 Miller indices

1.2 Planes and directions

1.2.1 Cubic structures

2 Classification
o

2.1 Lattice systems

2.2 Atomic coordination

2.2.1 Close packing

2.3 Bravais lattices

2.4 Point groups

2.5 Space groups

3 Grain boundaries

4 Defects and impurities

5 Prediction of structure

6 Polymorphism

7 Physical properties

8 See also

9 References

10 External links

[edit] Unit cell

The crystal structure of a material or the arrangement of atoms within a given type of crystal
structure can be described in terms of its unit cell. The unit cell is a small box containing one or

more atoms, a spatial arrangement of atoms. The unit cells stacked in three-dimensional space
describe the bulk arrangement of atoms of the crystal. The crystal structure has a three
dimensional shape. The unit cell is given by its lattice parameters which are the length of the cell
edges and the angles between them, while the positions of the atoms inside the unit cell are
described by the set of atomic positions (xi , yi , zi) measured from a lattice point.

Simple cubic (P)

Body-centered cubic (I)

Face-centered cubic (F)

[edit] Miller indices
Main article: Miller index

Planes with different Miller indices in cubic crystals

Vectors and atomic planes in a crystal lattice can be described by a three-value Miller index
notation (mn). The , m and n directional indices are separated by 90, and are thus orthogonal.
In fact, the component is mutually perpendicular to the m and n indices.
By definition, (mn) denotes a plane that intercepts the three points a1/, a2/m, and a3/n, or some
multiple thereof. That is, the Miller indices are proportional to the inverses of the intercepts of
the plane with the unit cell (in the basis of the lattice vectors). If one or more of the indices is
zero, it simply means that the planes do not intersect that axis (i.e. the intercept is "at infinity").
Considering only (mn) planes intersecting one or more lattice points (the lattice planes), the
perpendicular distance d between adjacent lattice planes is related to the (shortest) reciprocal
lattice vector orthogonal to the planes by the formula:

[edit] Planes and directions

The crystallographic directions are fictitious lines linking nodes (atoms, ions or molecules) of a
crystal. Similarly, the crystallographic planes are fictitious planes linking nodes. Some directions
and planes have a higher density of nodes. These high density planes have an influence on the
behavior of the crystal as follows:

Optical properties: Refractive index is directly related to density (or periodic

density fluctuations).

Adsorption and reactivity: Physical adsorption and chemical reactions occur

at or near surface atoms or molecules. These phenomena are thus sensitive
to the density of nodes.

Surface tension: The condensation of a material means that the atoms, ions
or molecules are more stable if they are surrounded by other similar species.
The surface tension of an interface thus varies according to the density on
the surface.

Dense crystallographic planes

Microstructural defects: Pores and crystallites tend to have straight grain

boundaries following higher density planes.

Cleavage: This typically occurs preferentially parallel to higher density

planes.

Plastic deformation: Dislocation glide occurs preferentially parallel to higher

density planes. The perturbation carried by the dislocation (Burgers vector) is
along a dense direction. The shift of one node in a more dense direction
requires a lesser distortion of the crystal lattice.

In the rhombohedral, hexagonal, and tetragonal systems, the basal plane is the plane
perpendicular to the principal axis.
[edit] Cubic structures

For the special case of simple cubic crystals, the lattice vectors are orthogonal and of equal
length (usually denoted a); similarly for the reciprocal lattice. So, in this common case, the
Miller indices (mn) and [mn] both simply denote normals/directions in Cartesian coordinates.
For cubic crystals with lattice constant a, the spacing d between adjacent (mn) lattice planes is
(from above):

Because of the symmetry of cubic crystals, it is possible to change the place and sign of the
integers and have equivalent directions and planes:

Coordinates in angle brackets such as <100> denote a family of directions

which are equivalent due to symmetry operations, such as [100], [010], [001]
or the negative of any of those directions.

Coordinates in curly brackets or braces such as {100} denote a family of

plane normals which are equivalent due to symmetry operations, much the
way angle brackets denote a family of directions.

For face-centered cubic (fcc) and body-centered cubic (bcc) lattices, the primitive lattice vectors
are not orthogonal. However, in these cases the Miller indices are conventionally defined relative
to the lattice vectors of the cubic supercell and hence are again simply the Cartesian directions.

[edit] Classification
The defining property of a crystal is its inherent symmetry, by which we mean that under certain
'operations' the crystal remains unchanged. For example, rotating the crystal 180 about a certain
axis may result in an atomic configuration which is identical to the original configuration. The
crystal is then said to have a twofold rotational symmetry about this axis. In addition to rotational
symmetries like this, a crystal may have symmetries in the form of mirror planes and
translational symmetries, and also the so-called "compound symmetries" which are a
combination of translation and rotation/mirror symmetries. A full classification of a crystal is
achieved when all of these inherent symmetries of the crystal are identified.[1]
[edit] Lattice systems

These lattice systems are a grouping of crystal structures according to the axial system used to
describe their lattice. Each lattice system consists of a set of three axes in a particular
geometrical arrangement. There are seven lattice systems. They are similar to but not quite the
same as the seven crystal systems and the six crystal families.
The 7 lattice
systems
(From least to
most symmetric)

The 14 Bravais Lattices

Exampl
es

1. triclinic
(none)

simple

base-centered

simple

base-centered

simple

body-centered

2. monoclinic
(1 diad)

3. orthorhombic
(3 perpendicular
diads)

4. rhombohedral
(1 triad)

5. tetragonal
(1 tetrad)

bodycentered

facecentered

6. hexagonal
(1 hexad)

simple (SC)

body-centered face-centered
(bcc)
(fcc)

7. cubic
(4 triads)

The simplest and most symmetric, the cubic (or isometric) system, has the symmetry of a cube,
that is, it exhibits four threefold rotational axes oriented at 109.5 (the tetrahedral angle) with
respect to each other. These threefold axes lie along the body diagonals of the cube. The other six
lattice systems, are hexagonal, tetragonal, rhombohedral (often confused with the trigonal crystal
system), orthorhombic, monoclinic and triclinic.
[edit] Atomic coordination

By considering the arrangement of atoms relative to each other, their coordination numbers (or
number of nearest neighbors), interatomic distances, types of bonding, etc., it is possible to form
a general view of the structures and alternative ways of visualizing then.

HCP lattice (left) and the fcc lattice (right).

[edit] Close packing

The principles involved can be understood by considering the most efficient way of packing
together equal-sized spheres and stacking close-packed atomic planes in three dimensions. For
example, if plane A lies beneath plane B, there are two possible ways of placing an additional
atom on top of layer B. If an additional layer was placed directly over plane A, this would give
rise to the following series :
...ABABABAB....

This type of crystal structure is known as hexagonal close packing (hcp).

If however, all three planes are staggered relative to each other and it is not until the fourth layer
is positioned directly over plane A that the sequence is repeated, then the following sequence
arises:
...ABCABCABC...

This type of crystal structure is known as cubic close packing (ccp)

The unit cell of the ccp arrangement is the face-centered cubic (fcc) unit cell. This is not
immediately obvious as the closely packed layers are parallel to the {111} planes of the fcc unit
cell. There are four different orientations of the close-packed layers.
The packing efficiency could be worked out by calculating the total volume of the spheres and
dividing that by the volume of the cell as follows:

The 74% packing efficiency is the maximum density possible in unit cells constructed of spheres
of only one size. Most crystalline forms of metallic elements are hcp, fcc, or bcc (body-centered
cubic). The coordination number of hcp and fcc is 12 and its atomic packing factor (APF) is the
number mentioned above, 0.74. The APF of bcc is 0.68 for comparison.
[edit] Bravais lattices

When the crystal systems are combined with the various possible lattice centerings, we arrive at
the Bravais lattices. They describe the geometric arrangement of the lattice points, and thereby
the translational symmetry of the crystal. In three dimensions, there are 14 unique Bravais
lattices which are distinct from one another in the translational symmetry they contain. All
crystalline materials recognized until now (not including quasicrystals) fit in one of these
arrangements. The fourteen three-dimensional lattices, classified by crystal system, are shown
above. The Bravais lattices are sometimes referred to as space lattices.

The crystal structure consists of the same group of atoms, the basis, positioned around each and
every lattice point. This group of atoms therefore repeats indefinitely in three dimensions
according to the arrangement of one of the 14 Bravais lattices. The characteristic rotation and
mirror symmetries of the group of atoms, or unit cell, is described by its crystallographic point
group.
[edit] Point groups

The crystallographic point group or crystal class is the mathematical group comprising the
symmetry operations that leave at least one point unmoved and that leave the appearance of the
crystal structure unchanged. These symmetry operations include

Reflection, which reflects the structure across a reflection plane

Rotation, which rotates the structure a specified portion of a circle about a

rotation axis

Inversion, which changes the sign of the coordinate of each point with respect
to a center of symmetry or inversion point

Improper rotation, which consists of a rotation about an axis followed by an

inversion.

Rotation axes (proper and improper), reflection planes, and centers of symmetry are collectively
called symmetry elements. There are 32 possible crystal classes. Each one can be classified into
one of the seven crystal systems.
[edit] Space groups

The space group of the crystal structure is composed of the translational symmetry operations in
addition to the operations of the point group. These include:

Pure translations which move a point along a vector

Screw axes, which rotate a point around an axis while translating parallel to
the axis

Glide planes, which reflect a point through a plane while translating it parallel
to the plane.

There are 230 distinct space groups.

[edit] Grain boundaries

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Grain boundaries are interfaces where crystals of different orientations meet. A grain boundary is
a single-phase interface, with crystals on each side of the boundary being identical except in
orientation. The term "crystallite boundary" is sometimes, though rarely, used. Grain boundary
areas contain those atoms that have been perturbed from their original lattice sites, dislocations,
and impurities that have migrated to the lower energy grain boundary.
Treating a grain boundary geometrically as an interface of a single crystal cut into two parts, one
of which is rotated, we see that there are five variables required to define a grain boundary. The
first two numbers come from the unit vector that specifies a rotation axis. The third number
designates the angle of rotation of the grain. The final two numbers specify the plane of the grain
boundary (or a unit vector that is normal to this plane).
Grain boundaries disrupt the motion of dislocations through a material, so reducing crystallite
size is a common way to improve strength, as described by the Hall-Petch relationship. Since
grain boundaries are defects in the crystal structure they tend to decrease the electrical and
thermal conductivity of the material. The high interfacial energy and relatively weak bonding in
most grain boundaries often makes them preferred sites for the onset of corrosion and for the
precipitation of new phases from the solid. They are also important to many of the mechanisms
of creep.
Grain boundaries are generally only a few nanometers wide. In common materials, crystallites
are large enough that grain boundaries account for a small fraction of the material. However,
very small grain sizes are achievable. In nanocrystalline solids, grain boundaries become a
significant volume fraction of the material, with profound effects on such properties as diffusion
and plasticity. In the limit of small crystallites, as the volume fraction of grain boundaries
approaches 100%, the material ceases to have any crystalline character, and thus becomes an
amorphous solid.

[edit] Defects and impurities

Real crystals feature defects or irregularities in the ideal arrangements described above and it is
these defects that critically determine many of the electrical and mechanical properties of real
materials. When one atom substitutes for one of the principal atomic components within the
crystal structure, alteration in the electrical and thermal properties of the material may ensue.[2]
Impurities may also manifest as spin impurities in certain materials. Research on magnetic
impurities demonstrates that substantial alteration of certain properties such as specific heat may
be affected by small concentrations of an impurity, as for example impurities in semiconducting
ferromagnetic alloys may lead to different properties as first predicted in the late 1960s.[3][4]
Dislocations in the crystal lattice allow shear at lower stress than that needed for a perfect crystal
structure.[5]

[edit] Prediction of structure

Main article: Crystal structure prediction

Crystal structure of sodium chloride (table salt)

The difficulty of predicting stable crystal structures based on the knowledge of only the chemical
composition has long been a stumbling block on the way to fully computational materials design.
Now, with more powerful algorithms and high-performance computing, structures of medium
complexity can be predicted using such approaches as evolutionary algorithms, random
sampling, or metadynamics.
The crystal structures of simple ionic solids (e.g. NaCl or table salt) have long been rationalized
in terms of Pauling's rules, first set out in 1929 by Linus Pauling, referred to by many since as
the "father of the chemical bond".[6] Pauling also considered the nature of the interatomic forces
in metals, and concluded that about half of the five d-orbitals in the transition metals are
involved in bonding, with the remaining nonbonding d-orbitals being responsible for the
magnetic properties. He therefore was able to correlate the number of d-orbitals in bond
formation with the bond length as well as many of the physical properties of the substance. He
subsequently introduced the metallic orbital, an extra orbital necessary to permit uninhibited
resonance of valence bonds among various electronic structures.[7]
In the resonating valence bond theory, the factors that determine the choice of one from among
alternative crystal structures of a metal or intermetallic compound revolve around the energy of
resonance of bonds among interatomic positions. It is clear that some modes of resonance would
make larger contributions (be more mechanically stable than others), and that in particular a
simple ratio of number of bonds to number of positions would be exceptional. The resulting
principle is that a special stability is associated with the simplest ratios or "bond numbers": 1/2,
1/3, 2/3, 1/4, 3/4, etc. The choice of structure and the value of the axial ratio (which determines

the relative bond lengths) are thus a result of the effort of an atom to use its valency in the
formation of stable bonds with simple fractional bond numbers.[8][9]
After postulating a direct correlation between electron concentration and crystal structure in betaphase alloys, Hume-Rothery analyzed the trends in melting points, compressibilities and bond
lengths as a function of group number in the periodic table in order to establish a system of
valencies of the transition elements in the metallic state. This treatment thus emphasized the
increasing bond strength as a function of group number.[10] The operation of directional forces
were emphasized in one article on the relation between bond hybrids and the metallic structures.
The resulting correlation between electronic and crystalline structures is summarized by a single
parameter, the weight of the d-electrons per hybridized metallic orbital. The d-weight
calculates out to 0.5, 0.7 and 0.9 for the fcc, hcp and bcc structures respectively. The relationship
between d-electrons and crystal structure thus becomes apparent.[11]

[edit] Polymorphism

Quartz is one of the several thermodynamically stable crystalline forms of silica,

SiO2. The most important forms of silica include: -quartz, -quartz, tridymite,
cristobalite, coesite, and stishovite.

Polymorphism refers to the ability of a solid to exist in more than one crystalline form or
structure. According to Gibbs' rules of phase equilibria, these unique crystalline phases will be
dependent on intensive variables such as pressure and temperature. Polymorphism can
potentially be found in many crystalline materials including polymers, minerals, and metals, and
is related to allotropy, which refers to elemental solids. The complete morphology of a material
is described by polymorphism and other variables such as crystal habit, amorphous fraction or

crystallographic defects. Polymorphs have different stabilities and may spontaneously convert
from a metastable form (or thermodynamically unstable form) to the stable form at a particular
temperature. They also exhibit different melting points, solubilities, and X-ray diffraction
patterns.
One good example of this is the quartz form of silicon dioxide, or SiO2. In the vast majority of
silicates, the Si atom shows tetrahedral coordination by 4 oxygens. All but one of the crystalline
forms involve tetrahedral SiO4 units linked together by shared vertices in different arrangements.
In different minerals the tetrahedra show different degrees of networking and polymerization.
For example, they occur singly, joined together in pairs, in larger finite clusters including rings,
in chains, double chains, sheets, and three-dimensional frameworks. The minerals are classified
into groups based on these structures. In each of its 7 thermodynamically stable crystalline forms
or polymorphs of crystalline quartz, only 2 out of 4 of each the edges of the SiO4 tetrahedra are
shared with others, yielding the net chemical formula for silica: SiO2.
Another example is elemental tin (Sn), which is malleable near ambient temperatures but is
brittle when cooled. This change in mechanical properties due to existence of its two major
allotropes, - and -tin. The two allotropes that are encountered at normal pressure and
temperature, -tin and -tin, are more commonly known as gray tin and white tin respectively.
Two more allotropes, and , exist at temperatures above 161 C and pressures above several
GPa.[12] White tin is metallic, and is the stable crystalline form at or above room temperature.
Below 13.2 C, tin exists in the gray form, which has a diamond cubic crystal structure, similar
to diamond, silicon or germanium. Gray tin has no metallic properties at all, is a dull-gray
powdery material, and has few uses, other than a few specialized semiconductor applications.[13]
Although the - transformation temperature of tin is nominally 13.2 C, impurities (e.g. Al, Zn,
etc.) lower the transition temperature well below 0 C, and upon addition of Sb or Bi the
transformation may not occur at all.[14]

[edit] Physical properties

Twenty of the 32 crystal classes are so-called piezoelectric, and crystals belonging to one of
these classes (point groups) display piezoelectricity. All piezoelectric classes lack a centre of
symmetry. Any material develops a dielectric polarization when an electric field is applied, but a
substance which has such a natural charge separation even in the absence of a field is called a
polar material. Whether or not a material is polar is determined solely by its crystal structure.
Only 10 of the 32 point groups are polar. All polar crystals are pyroelectric, so the 10 polar
crystal classes are sometimes referred to as the pyroelectric classes.
There are a few crystal structures, notably the perovskite structure, which exhibit ferroelectric
behavior. This is analogous to ferromagnetism, in that, in the absence of an electric field during
production, the ferroelectric crystal does not exhibit a polarization. Upon the application of an
electric field of sufficient magnitude, the crystal becomes permanently polarized. This

polarization can be reversed by a sufficiently large counter-charge, in the same way that a
ferromagnet can be reversed. However, it is important to note that, although they are called
ferroelectrics, the effect is due to the crystal structure (not the presence of a ferrous metal).