Crystal structure

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The (3-D) crystal structure of H2O ice Ih (c) consists of bases of H2O ice molecules (b) located on lattice points
within the (2-D) hexagonal space lattice (a). The values for the H–O–H angle and O–H distance have come
from Physics of Ice[1] with uncertainties of ±1.5° and ±0.005 Å, respectively. The white box in (c) is the unit cell
defined by Bernal and Fowler[2]

In crystallography, crystal structure is a description of the ordered arrangement

of atoms, ions or moleculesin a crystalline material.[3] Ordered structures occur from the intrinsic
nature of the constituent particles to form symmetric patterns that repeat along the principal
directions of three-dimensional space in matter.
The smallest group of particles in the material that constitutes the repeating pattern is the unit cell of
the structure. The unit cell completely defines the symmetry and structure of the entire crystal lattice,
which is built up by repetitive translation of the unit cell along its principal axes. The repeating
patterns are said to be located at the points of the Bravais lattice.
The lengths of the principal axes, or edges, of the unit cell and the angles between them are
the lattice constants, also called lattice parameters. The symmetry properties of the crystal are
described by the concept of space groups.[3] All possible symmetric arrangements of particles in
three-dimensional space may be described by the 230 space groups.
The crystal structure and symmetry play a critical role in determining many physical properties, such
as cleavage, electronic band structure, and optical transparency.

Contents

 1Unit cell
o 1.1Miller indices
o 1.2Planes and directions
 1.2.1Cubic structures
o 1.3Interplanar spacing
 2Classification by symmetry
o 2.1Lattice systems
 2.1.1Bravais lattices
o 2.2Crystal systems
 2.2.1Point groups
o 2.3Space groups
 3Atomic coordination
o 3.1Close packing
 4Grain boundaries
 5Defects and impurities
 6Prediction of structure
 7Polymorphism
 8Physical properties
 9See also
 10References
 11External links

Unit cell[edit]
Crystal structure is described in terms of the geometry of arrangement of particles in the unit cell.
The unit cell is defined as the smallest repeating unit having the full symmetry of the crystal
structure.[4] The geometry of the unit cell is defined as a parallelepiped, providing six lattice
parameters taken as the lengths of the cell edges (a, b, c) and the angles between them (α, β, γ).
The positions of particles inside the unit cell are described by the fractional coordinates (xi, yi, zi)
along the cell edges, measured from a reference point. It is only necessary to report the coordinates
of a smallest asymmetric subset of particles. This group of particles may be chosen so that it
occupies the smallest physical space, which means that not all particles need to be physically
located inside the boundaries given by the lattice parameters. All other particles of the unit cell are
generated by the symmetry operations that characterize the symmetry of the unit cell. The collection
of symmetry operations of the unit cell is expressed formally as the space group of the crystal
structure.[5]

Simple cubic (P)

Body-centered cubic (I)

 

Face-centered cubic (F)

Miller indices[edit]

Planes with different Miller indices in cubic crystals

Vectors and planes in a crystal lattice are described by the three-value Miller index notation. This
syntax uses the indices ℓ, m, and n as directional orthogonal parameters, which are separated by
90°.[6]
By definition, the syntax (ℓmn) denotes a plane that intercepts the three points a1/ℓ, 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
means that the planes do not intersect that axis (i.e., the intercept is "at infinity"). A plane containing
a coordinate axis is translated so that it no longer contains that axis before its Miller indices are
determined. The Miller indices for a plane are integers with no common factors. Negative indices are
indicated with horizontal bars, as in (123). In an orthogonal coordinate system for a cubic cell, the
Miller indices of a plane are the Cartesian components of a vector normal to the plane.
Considering only (ℓmn) planes intersecting one or more lattice points (the lattice planes), the
distance d between adjacent lattice planes is related to the (shortest) reciprocal lattice vector
orthogonal to the planes by the formula

Planes and directions[edit]

The crystallographic directions are geometric lines linking nodes (atoms, ions or molecules) of a
crystal. Likewise, the crystallographic planes are geometric 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:[3]

 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.
Some directions and planes are defined by symmetry of the crystal system. In monoclinic,
rhombohedral, tetragonal, and trigonal/hexagonal systems there is one unique axis (sometimes
called the principal axis) which has higher rotational symmetry than the other two axes.
The basal plane is the plane perpendicular to the principal axis in these crystal systems. For
triclinic, orthorhombic, and cubic crystal systems the axis designation is arbitrary and there is no
principal axis.
Cubic structures[edit]
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 (ℓmn) and [ℓmn] both simply denote normals/directions in Cartesian coordinates. For
cubic crystals with lattice constant a, the spacing d between adjacent (ℓmn) 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 that 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
that 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.
Interplanar spacing[edit]
The spacing d between adjacent (hkl) lattice planes is given by:[7]
Classification by symmetry[edit]
Main article: Crystal system
The defining property of a crystal is its inherent symmetry, by which we mean that under
certain 'operations' the crystal remains unchanged. All crystals have translational symmetry
in three directions, but some have other symmetry elements as well. For example, rotating
the crystal 180° about a certain axis may result in an atomic configuration that 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.[8]
Lattice systems[edit]
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
geometric arrangement. There are seven lattice systems. They are similar to but not quite
the same as the seven crystal systems.

14 Bravais Lattices
Crystal Lattice Schönflie
family system s
Base- Body- Face-
Primitive
centered centered centered

triclinic Ci

monoclinic C2h
 orthorhombic D2h

tetragonal D4h

rhombohedr
D3d
al

hexagon
al

hexagonal D6h

cubic Oh

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.
Bravais lattices[edit]
Main article: Bravais lattice
Bravais lattices, also referred to as space lattices, describe the geometric arrangement of
the lattice points,[6] and therefore the translational symmetry of the crystal. The three
dimensions of space afford 14 distinct Bravais lattices describing the translational symmetry.
All crystalline materials recognized today, not including quasicrystals, fit in one of these
arrangements. The fourteen three-dimensional lattices, classified by lattice system, are
shown above.
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 Bravais lattices. The characteristic
rotation and mirror symmetries of the unit cell is described by its crystallographic point
group.
Crystal systems[edit]
A crystal system is a set of point groups in which the point groups themselves and their
corresponding space groups are assigned to a lattice system. Of the 32 point groups that
exist in three dimensions, most are assigned to only one lattice system, in which case the
crystal system and lattice system both have the same name. However, five point groups are
assigned to two lattice systems, rhombohedral and hexagonal, because both lattice systems
exhibit threefold rotational symmetry. These point groups are assigned to the trigonal crystal
system.
In total there are seven crystal systems: triclinic, monoclinic, orthorhombic, tetragonal,
trigonal, hexagonal, and cubic.
Point groups[edit]
Main article: Crystallographic point group
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.
Space groups[edit]
Main article: Space group
In addition to the operations of the point group, the space group of the crystal structure
contains translational symmetry operations. 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.[9]
 Glide planes, which reflect a point through a plane while translating it parallel to the
plane.[9]
There are 230 distinct space groups.

Atomic coordination[edit]
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 them.[10]
Close packing[edit]
 The hcp lattice (left) and the fcc lattice (right)

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 arrangement of atoms in a 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 structural arrangement is known as cubic close packing (ccp).
The unit cell of a ccp arrangement of atoms 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 can be worked out by calculating the total volume of the
spheres and dividing 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 atoms in hcp and fcc structures is 12 and its atomic packing
factor (APF) is the number mentioned above, 0.74. This can be compared to the
APF of a bcc structure, which is 0.68.

Grain boundaries[edit]
Grain boundaries are interfaces where crystals of different orientations
meet.[6] 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).[10]
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.[10]
Grain boundaries are in general 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.[10]

Defects and impurities[edit]

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.[11] 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.[12][13] Dislocations in the crystal lattice allow shear at
lower stress than that needed for a perfect crystal structure.[14]

Prediction of structure[edit]
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".[15] 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.[16]
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.[17][18]
After postulating a direct correlation between electron concentration and crystal
structure in beta-phase 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.[19] 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.[20]
In crystal structure predictions/simulations, the periodicity is usually applied,
since the system is imagined as unlimited big in all directions. Starting from a
triclinic structure with no further symmetry property assumed, the system may
be driven to show some additional symmetry properties by applying Newton's
Second Law on particles in the unit cell and a recently developed dynamical
equation for the system period vectors [21] (lattice parameters including angles),
even if the system is subject to external stress.

Polymorphism[edit]

Quartz is one of the several crystalline forms of silica, SiO2. The most important
forms of silica include: α-quartz, β-quartz, tridymite, cristobalite, coesite,
and stishovite.

Polymorphism is the occurrence of multiple crystalline forms of a material. It is

found in many crystalline materials including polymers, minerals, and metals.
According to Gibbs' rules of phase equilibria, these unique crystalline phases
are dependent on intensive variables such as pressure and temperature.
Polymorphism 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 the 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, α- and β-tin. The two allotropes that
are encountered at normal pressure and temperature, α-tin and β-tin, are more
commonly known as gray tin and white tin respectively. Two more allotropes, γ
and σ, exist at temperatures above 161 °C and pressures above several
GPa.[22] 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.[23] Although the α–β
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.[24]

Physical properties[edit]
Twenty of the 32 crystal classes are piezoelectric, and crystals belonging to one
of these classes (point groups) display piezoelectricity. All piezoelectric classes
lack a center of symmetry. Any material develops a dielectric polarization when
an electric field is applied, but a substance that 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, although they are called ferroelectrics,
the effect is due to the crystal structure (not the presence of a ferrous metal).