, (1.1.1)
if
(r
z
r
O
Figure 1.1.1 The Cartesian coordinate system (x, y, z) and cylindrical coordinate system (, , z).
In the 3D Cartesian coordinate system (see Fig. 1.1.1), the transformation of coordinates may
be expressed as
r(x, y, z) r
(x
, y
, z
). (1.1.3)
In general, the transformation of coordinates may be decomposed into two parts: a matrix M
denoting an operation without translation such as a rotation about a xed axis or reection by
mirror, plus a translation vector t, i.e.,
r
= gr = Mr + t, M = (a
ij
) =
_
_
a
11
a
12
a
13
a
21
a
22
a
23
a
31
a
32
a
33
_
_
, (1.1.4)
or, expressed in components,
x
i
=
j
a
ij
x
j
+t
i
. (1.1.5)
A restricted set of symmetry operations satises the condition for isometry, i.e., the constancy of
the distance between any two points in the body under the symmetry transformation
r r
 =
_
(x
x)
2
+ (y
y)
2
+ (z
z)
2
, (1.1.6)
and the preservation of the angles between lines and planes during the transformation. In this
chapter we mainly deal with the symmetry operations that satisfy the condition of isometry, while
in 1.5.3 we shall mention those symmetry operations that violate this condition, e.g., ination or
deation related to the scale invariance, which will be treated more fully in Chap. 4.
For point symmetry, the determinant of the transformation is
M = a
ij
 = 1. (1.1.7)
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29 1.1 Basic Concepts of Symmetry
Consider a rotation about the zaxis from to
. If we let =
=
N
.
(2) Kaleidoscope theorem
The line of intersection of two mirror planes m and m
(see Fig. 1.1.5). This is the theoretical foundation of the toy kaleidoscope. If the space
between two mirrors at an angle of 30
A
B
C
D
A'
B'
A''
B''
C ''
D ''
A'''
B'''
C'''
D'''
T T ''
T'''
m
~
N
_
Figure 1.1.4 The demonstration of equivalence of mirror rotation
N and inversion rotation
N
( = ).
T T '
T''
/2
m'
m
Figure 1.1.5 The demonstration of the
kaleidoscope theorem.
A
A'
A''
m
m''
A'''
2
/2
N
3
N
2
N
1
O
m'
3
/2
1
/2
Figure 1.1.6 The demonstration of
the Euler theorem.
(3) Identity element
There is an identity element e G, such that for any g
i
G, eg
i
= g
i
.
(4) Inverse element
There is an inverse element g
1
i
for any g
i
G, such that g
i
g
1
i
= e.
From the axioms above, we shall get the uniqueness of the identity element and the inverse
element, i.e., eg
i
= g
i
e, g
i
g
1
i
= g
1
i
g
i
. In general, g
i
g
j
= g
j
g
i
, i.e., group elements are non
commutative; only in the special case of Abelian groups are every pair of elements commutative,
i.e., g
i
g
j
= g
j
g
i
. The number of distinct elements of the group is called the order of the group. If
the order of a group is nite, it is a nite or discrete group; if the order of a group is innite, it
is an innite or continuous group. We may easily verify that symmetry elements of a gure satisfy
these group axioms. Since successive rotations along axes pointing to dierent directions are non
commutative, so symmetry groups are in general nonAbelian; however, successive rotations along
the same axis are commutative, i.e., the result does not depend on the sequence of rotations, so
some symmetry groups may be Abelian. From the elements g
i
(i = i, . . . , n) of group G, we may
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32 Chapter 1. Symmetry of Structure
Figure 1.1.7 A NH3 molecule with its
rotation axis and mirror planes.
(a) (b)
Figure 1.1.8 The symmetry of circles.
(a) With arrowhead; (b) without arrowhead.
choose a subset of elements g
k
(k = 1, . . . , m, m < n), which itself forms a group G
, i.e., it satises
all group axioms, so it is called a subgroup of G. The order of the subgroup G
b
(m
b
)
b
(m
b
) c(mc) a(ma) C
2
3
(3
2
) E(1) C
1
3
(3
1
)
c(mc) c(mc) a(ma)
b
(m
b
) C
1
3
(3
1
) C
2
3
(3
2
) E(1)
1.1.4 Representations of Symmetry Groups
Each group has a characteristic multiplication table of its elements. These elements may be
expressed as numbers, symbols and functions with the same multiplication table. In the group G,
the elements of the subgroup G
can be expressed as e, g
2
, g
3
, . . . , g
n
, and the products of all of
them and some symmetry element g
x
in G but not belonging to G
x
multiplied from right side is called the right coset, while from left is called the left coset.
G
x
= eg
x
, g
2
g
x
, . . . , g
n
g
x
, (right coset);
g
x
G
= g
x
e, g
x
g
2
, . . . , g
x
g
n
, (left coset).
(1.1.13)
According to the concept of the coset, we shall get the group table which is called the exact (or
isomorphic) representation of the original group G. Usually we take the square matrix
M(G) =
_
_
_
_
_
a
11
a
12
. . . a
1n
a
21
a
22
. . . a
2n
.
.
.
.
.
.
.
.
.
.
.
.
a
n1
a
n2
. . . a
nn
_
_
_
_
_
= (a
ij
) (1.1.14)
to represent the symmetry operation of some vector, while the vector is the basis of the represen
tation. So the symmetry operation as introduced in 1.1.1 can be expressed by these operation
matrices as the representation of a group G. Here the a
ij
may be either a real number or a complex
one. So we may use multiplication of matrices to represent the multiplication of symmetry elements
of G. It may be easily seen that these representations fulll 4 group axioms introduced above, with
the identity matrix a
ij
= 1 (i = j), a
ij
= 0 (i = j). Any square matrix may be expressed in the
form
_
M
1
(A) M
2
(B)
M
1
(B) M
2
(A)
_
, (1.1.15)
where M
1
(A), M
1
(B), . . . are submatrices. If we can nd a transformation which makes M
1
(B) =
M
2
(B) = 0, then the original matrix can be reduced to matrices with lower rank, and it is called a
reducible representation; on the other hand, if it is impossible to nd a transformation which makes
M
1
(B) = M
2
(B) = 0, then the original matrix is called an irreducible representation. Generally,
we should reduce the group to its simplest form, i.e., the irreducible representation.
These rather abstract reasonings may be illustrated by some concrete examples: Take the group
C
3v
(3m) as an example of a nite group; take the 3D matrix introduced in 1.1.1 as 3D represen
tations, and r(x, y, z) as a basic vector. Select certain basis functions to simplify representations
into irreducible ones. Here we select z, (x, y) and R
z
as basis functions, R
z
indicates righthanded
(or lefthanded) screw along the z axis. We obtain two 1D representations for z and R
z
, one 2D
representation for (x, y) and they are all irreducible; they are tabulated in Table 1.1.2.
Table 1.1.2 The irreducible representation of C3v(3m).
C3v(3m) E(1) C
1
3
(3
1
) C
2
3
(3
2
) a(ma)
b
(m
b
) c(mc) Base
1 (1) (1) (1) (1) (1) (1) z
2 (1) (1) (1) (1) (1) (1) Rz
3
_
1 0
0 1
_ _
1
2
3
2
3
2
1
2
_ _
1
2
3
2
3
2
1
2
_ _
1 0
0 1
_ _
1
2
3
2
3
2
1
2
_ _
1
2
3
2
3
2
1
2
_
(x, y)
Now take group R(2) as an example of a continuous group. The matrix for the rotation can be
changed from 3D to 2D, so the original group may be replaced by its representations O(2) group,
i.e., the 2D group of orthogonal transformations with determinants equal to +1. It may be further
reduced to the 1D unitary group U(1), which has matrix M = exp(i) = cos + i sin . A matrix
is unitary if its Hermitian conjugate, M
= M
1
. If M is a matrix in
1D (i.e., with only one row and one column), then it is just a single number. This number must be
a complex number of the form exp(i) and its complex conjugate is exp(i). It should be noted
that the irreducible representation plays an important part in dealing with the electronic structure
of molecules and crystals using symmetry groups.
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34 Chapter 1. Symmetry of Structure
1.2 Finite Structures and Point Groups
Point groups describe the symmetry of nite gures, excluding translation as a symmetry element.
So all symmetry elements of a point group pass through a denite point, and the symmetries of most
molecules belong to this kind.
1.2.1 Combination Rules for Symmetry Axes
We now discuss the combination rules for symmetry axes along dif
N
1
N
4
N
2
N
3
2
Figure 1.2.1 The combina
tion of the symmetry axes
at dierent directions (emer
gences of symmetry axes at
the sphere surface form a
spherical triangle).
ferent directions. If there are two axes N
1
and N
2
, then a third axis
N
3
is expected according to the Euler theorem. Their emergent points
on a sphere will form a spherical triangle, and the entire sphere will be
divided into such triangles (see Fig. 1.2.1). The angles at the vertices of
these triangles are denoted by
i
equal to one half of the rotation angle
of the corresponding axis, i.e., 2/2N
i
. The sum of the inner angles of
a spherical triangle must exceed , therefore
1
N
1
+
1
N
2
+
1
N
3
> 1 . (1.2.1)
I II IIIa IIIb IV Va Vb VI VIIa
NC
n
N/2D
n
NS
n
(C
ni
) N/mC
nh N
m
C
nv
NmD
nd
N/mmD
nh
N
1
N
2
N
1
N
2

1
2
3
4
5
6
C
1
C
2
C
3
C
4
C
5
C
6
D
1
D
2
D
3
D
4
D
5
D
6
2
222
32
422
52
622
C
i
C
2i
C
3i
S
4
C
5i

1

3

4

5
m
C
2h
C
3h
C
4h
C
5h
C
6h
2/m

6
4/m

10
6/m
C
1v
C
2v
C
3v
C
4v
C
5v
C
6v
m
mm2
3m
4mm
5m
6mm
2/m C
2h
D
2d
D
5d
D
3d

42m

5m

3m
C
1h
D
2h
D
3h
D
4h
D
5h
D
6h
mm2
mmm

6m2
4/mmm

10m2
6/mmm
T 23
O 432
Y 235
T
h
O
h
Y
h

m3

m3m

m35
T
d

43m
2 /m mm /mm m
VIIb
N
1
N
2

Figure 1.2.2 The schematic diagram of point groups (showing the special arrangement of symmetry
elements by stereograms).
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35 1.2 Finite Structures and Point Groups
From this inequality we may enumerate all the possible cases of combinations of rotation axes: (1)
only one axis of high order N
3
= N 3 then N
1
= N
2
= 2, and all the combinations [N22] are
possible; where N may be any integer; (2) two or more axes of high order, the only possibilities
for [N
1
, N
2
, N
3
] are [233], [234], and [235]. This seemingly formidable problem of crystallography
(including quasicrystallography) is resolved at one stroke with a little geometry. Nfold axes with
N = 5 and N 6, though excluded from ordinary crystallography, are basic ingredients of qua
sicrystallography. Thus, the consequences of these combination rules can help us understand why
3D quasicrystals only have icosahedral symmetry [235], and there is no restriction on the order of
2D quasicrystals from the theory of symmetry.
1.2.2 Cyclic and Dihedral Groups
We have already mastered enough knowledge to derive all kinds of point groups. We have shown
that point symmetry elements may be divided into two types, type I contains only proper rotations
(including the identity), while type II contains improper rotations as well as mirror reections and
inversion. Now we are only concerned with point groups with only one Nfold rotation axis. We begin
with simple cyclic groups with Nfold axis without any type II symmetry elements, in International
notation, denoted by N; in Schonies notation, denoted by C
n
. Next we should consider point
groups related to the combinations of axes [N22], i.e., dihedral groups. Further, the addition of
type II symmetry elements may lead to more complex groups: groups (S
n
) with a simple improper
rotation axis
N; groups with an additional mirror plane perpendicular to the proper rotation axis,
i.e., N/m or C
nh
; groups with additional mirror planes bisecting two intersecting axes Nm and
Nm,
or C
nv
; similar operations may be acting on dihedral groups, making D
n
D
nh
and D
n
D
nd
.
These results are all tabulated in Fig. 1.2.2. Groups with more than one high order rotational axes
will be discussed in the next subsection.
1.2.3 Platonic Solids and Cubic Groups
To discuss point groups with more than one high order rotational axis, we shall review the
problems of the solid geometry of the regular polyhedra. There are ve regular polyhedra called
Platonic solids, from the era of Plato. A regular polyhedron, since all its faces are identical, is
characterized by a polygon with p faces; all vertices are also identical, each is connected to q polygons.
So we may use the Schlai notation {p, q} to denote a regular polyhedron. Thus ve Platonic
solids are (see Fig. 1.2.3) tetrahedron (4 regular equilateral triangular faces), {3, 3}; cube (6 square
faces), {4, 3}; octahedron (8 equilateral triangular faces), {3, 4}; dodecahedron (12 regular pentagon
faces), {5, 3}; icosahedron (20 regular triangular faces), {3, 5}. It should be noted that some pairs
of dierent regular polyhedra (for example octahedron and cube, icosahedron and dodecahedron)
belong to the same symmetry group. These pairs are related by dualities, which means the exchange
of the numbers of faces and vertices, i.e., the exchange of p, q values; the exchange of {3, 4} and
{3,3} {3,4} {4,3}
{5,3} {3,5}
Figure 1.2.3 Five kinds of regular polyhedron.
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36 Chapter 1. Symmetry of Structure
{4, 3} or {3, 5} and {5, 3}. Theatatus, a mathematician of ancient Greece, proved that there are
only 5 regular polyhedra in existence. The proof may be stated simply: A regular polygon can be
regarded as p vectors joined in a sequence but having the sum 0, and the angle between the two
joined vectors is the external angle of a polygon, so the sum of all the angles equals to 2. Every
external angle is 2/p, while the internal angle of a polygon is equal to (12/p). Now we consider
at each vertices of a polyhedron, the sum of internal angles of polygons connected to it must be less
than 2, since the polyhedron is convex, so an inequality is obtained
1
p
+
1
q
>
1
2
, (1.2.2)
or
(p 2)(q 2) < 4. (1.2.3)
It can be easily found that p and q have only combinations of {3, 3}, {3, 4} and {3, 5}, which
correspond to {3, 3}, {3, 4}, {4, 3}, {3, 5}, and {5, 3} of the Platonic solids. This purely geometrical
conclusion obtained 2000 years ago, was a prelude to the Euler theorem about the combination of
high order rotational axes of the modern theory of symmetry.
To enumerate the symmetry groups of Platonic solids, we shall begin with their rotational sub
groups T(23), O(432) and Y (235). For a tetrahedron, there are 4 threefold rotation axes passing
through the center to vertices, and 3 twofold rotation axes passing through the center to the cen
ters of the edges; for a regular octahedron, there are 3 fourfold rotation axes passing through the
center to the vertices, 4 threefold rotation axes passing through the centers of the triangular faces,
and 6 twofold rotation axes passing through the center to the centers of the edges; for a regular
icosahedron, there are 6 vefold axes passing through the center to the vertices, 10 threefold axes
passing through the center to the centers of triangular faces, and 15 twofold axes passing through
the center to the centers of the edges. These rotational subgroups are all composed of the I kind
of symmetry element. We shall introduce the II kind of symmetry element, reection, to obtain
higher order symmetry groups. For example from the Tgroup, 3 mirror planes perpendicular to
the 2fold axes may be added, thus T(23) T
h
(
2
m
43
2
m
); for the octahedral group O(432), mirror
planes perpendicular to 3 4fold axes and 6 2fold ones may be added, thus O(432) O
h
(
4
m
3
2
m
); for
Y (235), mirror planes perpendicular to 15 2fold axes may be added, making Y (235) Y
h
(
2
m
5).
All vertices of a regular polyhedron are situated on the same sphere, so the angles extended by
dierent axes (or faces) may be determined from the stereogram (see Fig. 1.2.4).
7
9
.2
5
8
.2
9
3
7
.
3
7
63.43
31.72
3
2
m
,
2
m
5.
It should be noted that the appearance of 3 or
3 in the second place is the criterion for cubic or
icosahedral symmetry. International notation may be written in abbreviated form, e.g.,
2
m
m, or
4
m
m in cubic symmetry, then
6
m
2
m
2
m
6
m
mm,
4
m
3
2
m
m
, obtuse
angle equal to 116.57
AA
from A to A
AA
to
bring A
to
A, bring A
to
B
BB
AA
, i.e.,
a + 2a sin(
2
) = a 2a cos = pa, (1.3.2)
then
cos =
(1 p)
2
. (1.3.3)
Satisfying 1 cos 1, we get p = 3, 2, 1, 0; and = 2/N, where N = 2, 3, 4, 6. It is clear that
only rotation axes 1, 2, 3, 4, 6 (including true and improper ones) are compatible with periodic
structure. In other words, the point groups of crystal can only contain the compatible rotation axes
derived above. Crystalline point groups only include the rotation axes compatible with periodicity,
so there are 10 2D point groups, 32 3D point groups. Icosahedral point groups and other group
containing 5fold or more than 6fold rotation axes are incompatible with the periodic structure, so
these are excluded in traditional crystallography; they belong in quasicrystallography.
1.3.2 Bravais Lattices
Traditionally all the lattices in crystallography are called Bravais lattices. In 2D (Fig. 1.3.6), these
are: The oblique, rectangular, centered rectangular (rhombic), square, and hexagonal (triangular).
According to the dierent types of symmetry, it is easy to demonstrate that there are only ve 2D
Bravais lattices (translation groups), but for 3D, there are fourteen Bravais lattices. It should be
noted that, for periodic structures, besides operations of point symmetry, other symmetry operations
involving translations should be considered, they include: Pure translations, glide reections and
screw axes (rotations and inversionrotations). Pure translations can be easily understood, while
the other two, equivalent to a point symmetry operation plus some fractional lattice translation,
are more complex. Glide reections are usually related to translations of t/2, or t/4, where t is
the lattice vector along the glide plane; while Nfold screw rotation is related to translation vectors
t
= pl/N, where p is an integer number smaller than N, and l is the translation vector along the
rotation axis (see Figs. 1.3.4 and 1.3.5).
g
t
t'
Figure 1.3.4 The schematic diagram of a glide
reecting plane.
t'
l
=2/n
0
N
t
Figure 1.3.5 The schematic
diagram of a screw axis.
Centered lattices are associated with added symmetry operations, such as glide reections, screw
axis operations, etc. In 2D space, the additional operation of the centered lattices is obvious: When
compared with the noncentered rectangular lattice, the 2D centered one adds a set of parallel glide
reection lines (a plane changes into a line in the case of 2D), and the translation vector l equals
a/2, b/2, so its symmetry is dierent from the noncentered lattice (see Fig. 1.3.6). Although in 3D
space the symmetry of lattice is more complex than that of 2D space, the situation is quite similar.
14 Bravais lattices are divided into the 7 crystal systems: Triclinic, monoclinic, orthorhombic,
tetragonal, rhombohedral, hexagonal and cubic. The rhombohedral point group can be considered
as a special type of centered hexagonal lattice. If we choose this viewpoint, the 7 crystal systems
are reduced to 6 (see Fig. 1.3.7). It should be noted that the classication of the Bravais lattices is
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40 Chapter 1. Symmetry of Structure
a
1
a
2
a
2
a
1
90
a
1
a
2
90
90
a
a
a
a
60
(a) (b)
(c) (d) (e)
Figure 1.3.6 The 2D Bravais lattices: (a) Oblique; (b) rectangular; (c) rhombic; (d) square; (e) hexagonal.
P I C F R
Type of Lattices
Crystal System
Related Point
Group
Triclinic
Monoclinic
Orthorhombic
Tetragonal
Hexagonal
Rhombohedral
Cubic
1, 1
2, m,
2
m
222, 2mm,
2
m
2
m
2
m
(mmm)
4, 4,
4
m
422,
4mm, 4 2m,
4
m
2
m
2
m
(4/mmm)
6,
3
m
,
6
m
,622,
6mm, 6 2 m,
6
m
2
m
2
m
(6/mmm)
3, 3, 32, 3m,
3
2
m
(3m)
23,
2
m
(3m), 3
432, 43m,
4
m
3
2
m
(m3m)
=
=/ a b c =/
90
=/ =/ =/
=/ a b c =/
= = 90
90
=/
=/ a b c =/
90
= = =
= a b c =/
90
= = =
= a b c =/
= = 90
120
=
= a b c =
90
= = =/
90
= = =
= a b c =
P (Primitive ) , I (Body Center) , C (Bottom Center), F (Face Center), R (Rhombohedron)
Figure 1.3.7 14 kinds of Bravais lattices.
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41 1.3 Periodic Structures and Space Groups
carried out by the dierences in symmetry, so the types of the lattices coincide with the translation
groups, i.e., the groups of pure translations.
1.3.3 Space Groups
In the early 1890s, Fedorov and Schonies independently enumerated 230 space groups as a
crowning achievement of classical crystallography. Fedorovs approach was more geometrical and
intuitive, while Schonies approach was more mathematical and exact. However it is too tedious
to repeat all these arguments leading to the nal result. Here we shall take a far simpler case, 2D
space groups or plane groups for a brief discussion.
As we know, there are 5 Bravais lattices. We may generate 13 symmorphic groups by combining
each Bravais lattice with compatible point groups. The only nonsymmorphic operation permitted in
2D is the glide with reection across a line in the ab plane, and a further 4 nonsymmorphic groups
are generated, making a total of 17 in all. These may be used to classify surface structures (see
Fig. 1.3.8).
Figure 1.3.8 17 kinds of 2D space groups. (a) The arrangement of symmetry elements; (b) the typical
patterns for these group.
In the case of 3D, the situation is the same, although more complicated. The nonsymmorphic
symmetry operations include glidereections and screwrotations, both involving suitable fractions
of lattice translations. 73 symmorphic groups may be generated by combining Bravais lattices
with compatible point groups, while 157 nonsymmorphic groups may be generated involving the
nonsymmorphic symmetry operations. In fact, the nonsymmorphic symmetry operations play a
more important role in 3D space, which makes the theory of space groups quite complex. Among
space groups, there are 11 pairs of enantiomorphic space groups, i.e., one of them can be obtained
by a mirror image of another, like left and right hands. For instance, P6
2
22 is the space group for
right hand quartz, and while P6
4
22 is that for left hand quartz. Determination of the space group is
a primary step in a full structure determination. Centered lattices and nonsymmorphic symmetry
elements may be recognized by systematic extinctions in Xray diraction patterns. Whether an
inversion center exists or not should be determined by supplementary physical tests, for instance,
second harmonic generation of laser light, piezoelectricity or the anomalous dispersion of Xray
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42 Chapter 1. Symmetry of Structure
diraction. The last method is based on the breakdown of the Friedel rule for the Xray diraction
intensity of a pair of reections, i.e., I(h, k, l) = I(
h,
k,
l).
1.3.4 The Description of Crystal Structure
In the study of specic substances, scientists usually need knowledge of the crystal structure. A
complete description of the crystal structure includes lattice parameters and the type and coordinates
of each atom in the unit cell. Often, familiar crystal structures can be found in reference books,
but usually the data given in the literature are in shorthand form (such as the Wycko symbol).
The space group table in the International Tables for Crystallography should be consulted for the
full elucidation of the structure. Here we give an example of the use of the International Tables for
Crystallography, Vol. I for LiNbO
3
.
Chemical formula: LiNbO
3
;
Lattice: Rhombohedrallycentered hexagonal with a = 5.448
A, c = 13.863
A;
Number of chemical formula in a unit cell: 6;
Space group: R3c (No.161);
Atomic coordinates: Nb in 6(a): 0, 0, w
1
(w
1
= 0.0186); Li in 6(a): 0, 0,
1
3
w
2
(w
2
= 0.0318);
O in 18(b): x, y, z (x = 0.0492, y = 0.3446, z = 0.0833).
With the information provided by the original paper on the determination of the crystal structure
of LiNbO
3
, we shall nd all the atomic positions by choosing the hexagonal coordinate on the page
containing the R3c space group in the International Tables.
Position of the lattice point: (0, 0, 0;
1
3
,
2
3
,
2
3
;
2
3
,
1
3
,
1
3
)
Wycko symbol: (a) 6 positions: 0, 0, z; 0, 0,
1
2
+ z;
(b) 18 positions: x, y, z; y, x y, z; y x, x, z; y, x,
1
2
+ z;
x, x y,
1
2
+ z; y x, y,
1
2
+ z.
From the positions of (a), (b) and its extention by the three lattice points, we shall derive all the
atomic positions: Nb, Li atoms occupying positions (a), and atoms O occupying positions (b), the
resulted crystal structure is shown schematically in Fig. 1.3.9.
0,0
2
3
1
3 ,
0,0
8
10
0
2
4
6
8
Nb Li
1
1
1
1
1
3
3
3
3
3
5
5
5
5
5
7
7
7
7
7
9
9
9
9
9
11
11
11
11
11
x
y
(a)
A
A
A
A
B
C
(c) (b)
2
3
1
3 ,
Figure 1.3.9 The structure of LiNbO3. (a) Nb, Li atoms are placed on (11
1
[(k)] =
1
2
_
(k) exp(ikx)dk = f(x) . (1.4.2)
It may be readily extended to functions in 3D space, for example, the distribution of density of
scattering centers in ordinary space,
(k) =
_
(r) exp(ik r)dr . (1.4.3)
From the inverse transform we may recover the original
1
[(k)] =
1
(2)
3
_
(k)exp(ik r)dk = (r) . (1.4.4)
Here k is an arbitrary vector with dimension [length]
1
called the reciprocal lattice vector. Let
vectors r and k be decomposed into their Cartesian components x, y, z and k
x
, k
y
, k
z
, so the inner
product of them is
k r = k
x
x +k
y
y +k
z
z . (1.4.5)
So, every structure has its reciprocal, i.e., its Fourier transform, which contains the full information
of the original structure. If the Fourier transform is thoroughly known, then the original structure
may be recovered easily by the inverse transform through calculation. The Fourier transform of a
structure is connected to the experimental results of wave scattering through the following relations.
We dene the incident wave vector K
0
and the scattering wave vector K with directions along the
beams and with magnitudes equal to the reciprocal wavelength
1
, then
k = K K
0
, (1.4.6)
so the scattering amplitude is proportional to the Fourier transform associated with k. In order to
observe dierent regions of reciprocal space, the incident and scattering directions, as well as the
wavelength of the incident radiation, may be changed. So the Fourier transform of a structure and
its inverse are closely related to the physical process of observation and determination of structure.
However, it should be noted that our knowledge of the Fourier transform of a structure is never
complete, for the wavelength of radiation used has nite value, there are always regions in reciprocal
space inaccessible to experimental probing, and most detectors cannot register the phase of radia
tion, so usually only the intensities instead of the amplitudes are recorded. These are fundamental
diculties for structure determination.
1.4.2 The Reciprocal Lattice
Next we shall show that the Fourier transform of a lattice gives the reciprocal lattice. Firstly let
consider the simplest case, the 1D lattice with period a dened by Diracs delta function (x ua),
u = 0, 1, 2, . . ., , satisfying
(x ua) =
_
, if x = ua,
0, otherwise,
(1.4.7)
and
_
(x ua)dx = 1 . (1.4.8)
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44 Chapter 1. Symmetry of Structure
The Fourier transform of this delta function is also a delta function
_
(x ua) exp(ikx)dx =
_
k
2u
a
_
. (1.4.9)
This delta function may be visualized as a series of planes perpendicular to the x axis with spacings
equal to 2/a (u = 0, 1, 2, . . . , ).
For a 3D lattice with basic vectors a, b and c,
l = ua +vb + wc, u, v, w = 0, 1, 2, . . . , . (1.4.10)
This may be written as a 3D delta function (r l), and its Fourier transform is readily found to be
(G) = (k G) . (1.4.11)
This 3D delta function dene a lattice, the reciprocal lattice, which may be visualized as the in
tersection points of 3 families of parallel planes which are parallel to the bcplane, acplane and
abplane with spacings equal to 2/a, 2/b and 2/c respectively. Mathematically the reciprocal
vector G is
G = ha
+kb
+lc
, (1.4.12)
where h, k, l = 0, 1, 2, . . . , , and
a
a = 2, b
b = 2, c
c = 2 . (1.4.13)
It can be also rewritten as
a
= 2b c/
0
, b
= 2c a/
0
, c
= 2a b/
0
, (1.4.14)
where
0
is the volume of a unit cell,
0
= a b c . (1.4.15)
If the basic vectors of the direct lattice are orthogonal to each other, then the directions of the
basis vectors of the reciprocal lattice coincide with those of the direct lattice. In general, a
may
deviate from a but is always perpendicular to the plane dened by b c. It should be noted that
the denition of the reciprocal lattice vector introduced here follows the convention adopted in texts
on solid state physics; it is slightly dierent from that commonly used in texts on crystallography,
in which the factors of 2 in (1.4.13) and (1.4.14) are replaced by unity, i.e., the relation appears to
be more symmetrical.
Now we shall examine whether Fourier transformation has an eect on this. We know that
there are 14 Bravais lattices and, besides primitive lattices, there are centered lattices, such as base
centered, bodycentered and facecentered. The reciprocal lattices of primitive lattices retain the
original lattice symmetry, but, the situation is dierent for centered lattices. It is easy to verify that
a facecentered direct lattice is transformed into a bodycentered reciprocal lattice and vice versa,
while basecentered lattices remain unchanged. The reciprocal lattice is an important concept in
condensed matter physics; it has played crucial roles in the physics of diraction as well as condensed
matter theories dealing with wave propagation in periodic structures.
1.4.3 Fourier Transform of Periodic Structure
The crystal structure may be understood as the content of the unit cell repeated by the lattice,
i.e., each lattice point is associated with a unit cell. Let the density distribution of a unit cell be
f(r), it is repeated at each lattice point, in the language of Fourier transform this act is called
convolution, denoted by f(r)(r l). According to the convolution theorem, the Fourier transform
of the convoluted function is simply the product of their respective transforms, i.e.,
_
f(r)(r l)exp(ikr)dr = F(k)(k G) , (1.4.16)
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45 1.5 Generalized Symmetry
here F(k) is the Fourier transform of f(r) and is usually called the structure factor in diraction
physics; it is a continuous function in reciprocal space. In an actual diraction experiment, the
absolute values of F(G) are sampled at the reciprocal lattice points G. We also dene the incident
wave vector K
0
and the scattering wave vector K (K = K
0
 = 2
1
), where is the wavelength
of the radiation), then
K K
0
= k = G. (1.4.17)
Because G = 2d
1
hkl
, the equation above is the generalized form of the Bragg equation (2d
hkl
sin =
). Now F(k) can be expressed by the reciprocal lattice points h, k, l, in the form F(h, k, l).
Here we use the kinematical theory of diraction, and ignore the interaction of the incident and the
scattering wave (see Fig. 1.4.1). We shall discuss the dynamical theory of diraction in 5.4.2.
Using the full spectrum of F(hkl) values (complex num
d
hkl
K
0
K
K
0
k
G

Figure 1.4.1 Bragg equation and recip
rocal vector.
bers) we may reach the goal of crystal structure analy
sis, i.e., the distribution of density of scattering matter
within the unit cell, by means of the inverse transform.
Let (, , ) be the fractional coordinates of a point in an
unit cell so that x = a, y = b, z = c, then
(, , ) =
1
hkl
F(h, k, l) exp[2i(h +k +l)] .
(1.4.18)
The problem is reduced to the summation of Fourier se
ries, which can be done in a straightforward fashion. How
ever, due to the fact that the phase of F(hkl) cannot be
determined directly from experiment, the phase problem
still remains a crucial question in crystal structure analysis.
Many ingenious methods have been developed to overcome
this diculty; in conjunction with enormous advances in
the calculating capability of modern electronic computers,
crystal structures of moderate complexity can be solved routinely. For problems related to crystal
structure analysis, readers should consult the texts on this special subject, such as Bibs. [5, 6].
1.5 Generalized Symmetry
Ordinary space has 3 dimensions and space groups give a complete description of its possible
symmetries. In this section we shall discuss the generalized symmetries beyond ordinary space
groups.
1.5.1 HighDimensional Space Groups
Mathematically it is not dicult to generalize the symmetry of 3D Euclidean space to Euclidean
spaces with dimensions higher than 3, the motivation for this generalization is to extract real physical
consequences from some of these nD symmetries. For instance, 4D space groups are used in the
study of incommensurate structures, while 6D space groups are used in the study of quasicrystals.
These, together with the problems related to the projections from the highdimensional spaces into
lowerdimensional ones, will be treated in 2.3.
1.5.2 Color Groups
Another dimension with discrete values may be added into an ordinary 3D space. These discrete
values may be expressed as dierent colors, so the symmetry groups of these spaces are called color
groups. The simplest color group is the blackwhite group. The idea of blackwhite symmetry or
antisymmetry may be introduced by inspecting Fig. 1.5.1 which shows a series of orthogonal mirror
planes with which black patterns are transformed into white ones, and vice versa.
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46 Chapter 1. Symmetry of Structure
Figure 1.5.1 A gure of blackwhite symmetry.
The black or white color may acquire dierent physical meanings in actual crystal structure,
such as up and down spin, positive and negative charges, etc., so the blackwhite group is equivalent
to the magnetic group, the symmetry groups of magnetically ordered structures. Obviously black
white groups are much complicated than ordinary space groups, the number of symmetry groups is
much larger (see Table 1.5.1). Blackwhite groups have only two colors, when the number of colors
is larger than 2, these are multicolored groups. Ions in crystals may have dierent orbitals with
nearly the same energy so in order to describe detailed distribution of these orbitals on a crystalline
lattice, multicolored groups are required.
Table 1.5.1 Comparison of ordinary symmetry and blackwhite symmetry for fully periodic symmetry.
Kind of sym Number of Number of groups
metry group dimensions ordinary 1color gray 2color total
1 1 1 1 2
Transition group 2 5 5 5 10
3 14 14 22 36
1 2 2 2 1 5
Point group 2 10 10 10 11 31
3 32 32 32 58 122
1 2 2 2 3 7
Space group 2 17 17 17 46 80
3 230 230 230 1191 1651
We may introduce complex symmetry elements to represent color groups. A complex symmetry
element is a combination of an ordinary 3D symmetry element g and a compatible symmetry
element on a complex plane , i.e., = (g, ). If a complex symmetry element is to operate on a
point r(x, y, z), then F(r) will multiplied by a phase factor i.e.,
F(gr) = F(r) exp[2i(r)], (1.5.1)
where (r) is the phase factor, and is the function of r.
Color groups with colors correspond to fold rotation, i.e.,
=
1
. (1.5.2)
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47 Bibliography
When = 2, = 1, these are the blackwhite groups as a special example; when = 1, = 1,
they become the ordinary space groups. Thus, the introduction of complex symmetry elements gives
a general way to derive color groups.
1.5.3 Symmetry of Reciprocal Space
Introduction of complex symmetry elements is indispensable to the study of the symmetry of
reciprocal space. Consider the case of periodic structure in direct space: The distribution of its
Fourier coecients, i.e., the structure factor F(h, k, l) = F(h, k, l) exp(2i), is limited to the
reciprocal lattice points (h, k, l). The distribution of matter in direct space is continuous, while
the distribution of Fourier coecients in reciprocal space is discontinuous, i.e., each lattice point is
weighted with its corresponding structure factor. Due to the weighed structure factor, reciprocal
space is no longer periodic. Thus, the space groups of direct space correspond to the complex point
groups of index space. So it gives another way to derive 230 space groups, i.e., to derive it from
complex point groups of index space.
In this case, symmetry operations of point group G will make (k) (gk), and
(gk) = (k) exp[2i
g
(k)] , (1.5.3)
where exp[2i
g
(k)] is called the phase function of the point group operation. With the introduction
of the phase function, the point group is enlarged. Actually the nonsymmorphic symmetric elements
of space group are implicitly contained in the phase function, for instance systematic extinction in
centered lattices. It is customary to prepare tables showing the eects due to the symmetric elements
of space group, now the way is reversed to derive space groups from complex point groups.
It should be noted that the functionlike Fourier transform is not limited to periodic structures.
The study of symmetry in reciprocal space may be extended to derive space groups of quasiperiodic
structure without invoking unphysical highdimensional space.
b
1.5.4 Other Extensions of Symmetry
According to the symmetry mentioned above, the structure should be the same after the sym
metry operation. Another generalization of the concept of symmetry is to replace identity by ap
proximate or statistical equality, i.e.,
F(gr) = F(r
) F(r). (1.5.4)
In this way we shall describe the statistical distribution of dierent kinds of atoms in alloy structure,
atomic positions in glasses and liquids, or the orientation distribution of rodlike molecules along a
given direction. This concept of statistical symmetry will be further discussed in Chap. 3.
Previously we have only considered symmetry operations that do not violate the condition of
isometry, i.e., the lengths, angles, areas, and volumes are preserved in the symmetry operations.
If we introduce a transformation by change of scale, such as deation or ination, a new type of
symmetry, i.e., scale invariance is introduced. This will be discussed more fully in Chap. 4.
Bibliography
[1] Weyl, H., Symmetry, Princeton University Press, Princeton (1952).
[2] Vainshtein, B. K., Modern Crystallography I, 2nd ed., SpringerVerlag, Berlin (1994).
[3] Burns, G., and A. M. Glasser, Space Groups for Solid State Scientists, 2nd ed., Academic Press,
New York (1990).
b
Introducing the complex symmetry elements and deriving the ordinary space groups from reciprocal space was begun
by A. Binenstock and P. P. Ewald, see A. Binenstock, P. P. Ewald, Acta. Cryst. 15, 1253 (1962). Later N. D. Mermin
derived the space groups of quasiperiodic structures, see D. A. Rabson, N. D. Mermin et al., Rev. Mod. Phys. 63,
699 (1991); N. D. Mermin, Rev. Mod. Phys. 64, 3 (1992).
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48 Bibliography
[4] Hahn, A. J., and A. J. Cochran, International Tables for Crystallography, Vol. A, Space Group
Symmetry, 3rd ed., Kluwer Academic Publishers, Dordrecht (1992).
[5] Lipson, H., and W. Cochran, The Determination of Crystal Structures, 3rd ed., G. Bell and Sons,
London (1966).
[6] Woolfson, M. M., and Fan Haifu, Physical and Nonphysical Methods of Solving Crystal Struc
tures, Cambridge University Press, Cambridge (1995).