Solid State Physics 2 Edition/ nd

Giuseppe Grosso

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
Chapter Outline
2.1 Simple Lattices and Composite Lattices
2.1.1 Periodicity and Bravais Lattices
2.1.2 Simple and Composite Crystal Structures
2.2 Geometrical Description of Some Crystal Structures
2.3 Wigner-Seitz Primitive Cells
2.4 Reciprocal Lattices
2.4.1 Definitions and Basic Properties
2.4.2 Planes and Directions in Bravais Lattices
2.5 Brillouin Zones

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
Chapter Outline
2.6 Translational Symmetry and Quantum Mechanical
Aspects
2.6.1 Translational Symmetry and Bloch Wavefunctions
2.6.2 The Parametric k · p Hamiltonian
2.6.3 Cyclic Boundary Conditions
2.6.4 Special k Points for Averaging Over the Brillouin Zone
2.7 Density-of-States and Critical Points

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.5 Brillouin Zones

Brillouin Zone for the Simple Cubic Lattice

• The fundamental vectors in direct space of a simple cubic
lattice are

• From Eqs. (2.17) we have

• Thus the reciprocal lattice is still a simple cube, with edge

2π/a.

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.5 Brillouin Zones

• The first Brillouin zone is indicated in Figure 2.17. Points

of high symmetry in the cubic Brillouin zone are indicated
by conventional letters: denotes the origin of the Brillouin
zone;

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.5 Brillouin Zones

Brillouin Zone for the Face-Centered Cubic Lattice

• The fundamental vectors for an fcc Bravais lattice are

• By applying Eqs. (2.17), we have for the fundamental

vectors of the reciprocal lattice

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.5 Brillouin Zones

• Thus the reciprocal lattice of an fcc lattice is a bcc lattice.

The Brillouin zone is the truncated octahedron shown in
Figure 2.18.

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.5 Brillouin Zones

Brillouin Zone for the Body-Centered Cubic Lattice

• The fundamental vectors for a bcc lattice in direct and
reciprocal space are

• The Brillouin zone is the regular rhombic dodecahedron

shown in Figure 2.19.

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.5 Brillouin Zones

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.5 Brillouin Zones

Brillouin Zone for the Hexagonal Lattice

• The fundamental translation vectors of the Bravais
hexagonal lattice are

• And the fundamental vectors of the reciprocal lattice are

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.5 Brillouin Zones

• Thus the reciprocal of the hexagonal lattice is still an

hexagonal lattice. The Brillouin zone is shown in Figure
2.20.

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.6 Translational Symmetry and
Quantum Mechanical Aspects
2.6.1 Translational Symmetry and Bloch Wavefunctions
• In this section, we consider the effect of periodicity in
actual three-dimensional crystals; for this purpose we
have already prepared the needed tools, in particular the
notion of Brillouin zone and reciprocal lattice.
Consider the Schrödinger equation

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.6 Translational Symmetry and
Quantum Mechanical Aspects
• For an electron in a periodic potential. Since V(r) has the
lattice periodicity, we can expand it in plane waves
characterized by reciprocal lattice vectors in the form

• The matrix elements of a periodic potential between

(normalized) plane waves of vectors k and kˊ are
different from zero only if the twowavevectors differ by a
reciprocal lattice vector. From expansion (2.27a) we have
in fact

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.6 Translational Symmetry and
Quantum Mechanical Aspects
• A crystal wavefunction ψ(k, r), of vector k, must be an
appropriate linear combination of plane waves of vectors
k+gn (this being the only kind of mixing allowed by a
periodic potential, and hence by the crystal Hamiltonian):

• Since the functions exp (ign · r) have the lattice periodicity,

Eq. (2.28) can be written in the form

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.6 Translational Symmetry and
Quantum Mechanical Aspects
• There is another equivalent way of expressing the Bloch
theorem, summarized by Eq. (2.29a). We notice that

• For any given k vector, we have in general a countably

infinite set of solutions; different solutions can be labeled
with an index, say n, following for instance the increasing
value of energy. Suppose to vary continuously k in the
first Brillouin zone and to follow the crystal eigenvalues
En(k) and the crystal wavefunctions ψn(k, r); we arrive
thus at the concept of the energy band structure of
electrons in crystals.
Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.6 Translational Symmetry and
Quantum Mechanical Aspects
2.6.2 The Parametric k · p Hamiltonian
• The general form of the Bloch wavefunctions, as the
product of a plane wave and a periodic part, allows
further general elaborations. We insert the Bloch form of
the wavefunctions into the Schrödinger equation (2.26)
and obtain

• Thus, the periodic parts un(k, r) of the electronic

wavefunctions satisfy the modified Schrödinger equation

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.6 Translational Symmetry and
Quantum Mechanical Aspects
• Following a Feynman procedure, we derive both
members of Eq. (2.30) with respect to the parameter k
and obtain

• The projection of Eq. (2.31) on um(k, r)| with m ≡ n gives

this relation can be expressed in the form

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.6 Translational Symmetry and
Quantum Mechanical Aspects
• Which is the trivial generalization of Eq. (1.73) to the
three-dimensional crystal. The projection of Eq. (2.31)
on um(k, r)| with m = n gives

• In many situations it is convenient, instead of the

momentum operator p, to evaluate the matrix elements of
the coordinate operator r. From standard commutation
rules it holds

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.6 Translational Symmetry and
Quantum Mechanical Aspects
• Taking thematrix elements of bothmembers of the above
equation between two crystal eigenfunctions one obtains

• Comparison of Eqs. (2.34) and (2.33) gives the relation

• We nowshow that the knowledge of the set of wavefunction

{ψn(k0, r)} and band energies En (k0) just at a single k0
vector implies the knowledge (at least in principle) of the
whole band structure (wavefunctions and energies) on the
entire Brillouin zone.
Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.6 Translational Symmetry and
Quantum Mechanical Aspects
• For sake of simplicity (and without loss of generality) we
select k0 at the center of the Brillouin zone (the arguments
below are readily applicable to any other selected point in
the Brillouin zone). A crystal wavefunction ψ(k, r) of
vector k can always be expanded in the form

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.6 Translational Symmetry and
Quantum Mechanical Aspects
• Thematrix elements of the crystalHamiltonian among the
functions {exp (ik·r)ψn0(r)} are

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.6 Translational Symmetry and
Quantum Mechanical Aspects
• From expansion (2.36a), matrix elements (2.36b), and
standard variational methods in the expansion
coefficients, we have that band energies and
bandwavefunctions at any wavevector k are obtained by
the eigenvalues and eigenvectors of the secular equation

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.6 Translational Symmetry and
Quantum Mechanical Aspects
• A most significant use of Eq. (2.37) is to confine k to a
small region of the Brillouin zone, around the point k = 0.
In this case the off-diagonal matrix elements in Eq. (2.37)
are small, and thus can be safely treated with standard
perturbation theory. Suppose, The perturbation theory for
non-degenerate states, up to second order in the wave-
vector, gives for the band energy En(k) the expression

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.6 Translational Symmetry and
Quantum Mechanical Aspects
• The right-hand side of Eq. (2.38) is a quadratic function
of the wavevector, and can be cast in the form

• Where the effective mass tensor reads

• Expression (2.39) gives for the effective masses of the

two bands

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.6 Translational Symmetry and
Quantum Mechanical Aspects
2.6.3 Cyclic Boundary Conditions
• Suppose now to have a macroscopic (but finite) crystal,
of volume V, in the form of a parallelepiped with edges
N1t1, N2t2, and N3t3, where N1, N2, N3 are large (but finite)
integer numbers. The Born-von Karman cyclic boundary
conditions on the electronic wavefunctions require

• Since ψ(r) must be a Bloch function of vector k, we have

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.6 Translational Symmetry and
Quantum Mechanical Aspects
• The possible k vectors, compatible with cyclic boundary
conditions (2.40), are thus

with mi integer numbers.

• The density of allowed k vectors (2.41) in the reciprocal
space is uniform and is given by

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.6 Translational Symmetry and
Quantum Mechanical Aspects
• Where V is the volume of the crystal. In some problems,
we have to perform sums in reciprocal space of a given
function of k. According to Eq. (2.42), the discrete sum
can be replaced by an integral as follows

where dk is the volume element in reciprocal space.

• Notice also that the k vectors (2.41)within the first
Brillouin zone satisfy the relation

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.6 Translational Symmetry and
Quantum Mechanical Aspects
• Where tn is any translation of the crystal such that 0 ≤ ni
< Ni (i = 1, 2, 3). The proof is simply based on the
elementary algebraic property that the sum of the Ni roots
of the unity equals zero. Similarly we have

where k is any vector (2.41) in the reciprocal space.

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.6 Translational Symmetry and
Quantum Mechanical Aspects
2.6.4 Special k Points for Averaging Over the Brillouin
Zone
• In several studies of crystals (for instance in the
calculation of charge density, total energies and other
properties) we have to perform the average of appropriate
k-dependent functions throughout the Brillouin zone. The
average value of a function F(k) is given by

• Where N is the (large) number of allowed k vectors in the

first Brillouin zone.
Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.6 Translational Symmetry and
Quantum Mechanical Aspects
• Consider a function F(k) with k defined in the first
Brillouin zone, or, equivalently, consider a function F(k)
with the periodicity of the reciprocal lattice; its most
general expansion, according to Eq. (2.19c) is

• Where tn are translation vectors of the direct lattice, Fn

are the appropriate Fourier coefficients, and for
convenience the tn = 0 term has been separated from all
the other terms.
Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.6 Translational Symmetry and
Quantum Mechanical Aspects
• Consider now a function G(k) represented in the form

• Where tI denotes translation vectors belonging to the first

shell of neighbors (all other Fourier coefficients are
assumed to be zero). Let {ks } indicate an appropriately
selected set of ns points of the Brillouin zone, chosen in
such a way that

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices
2.6 Translational Symmetry and
Quantum Mechanical Aspects
• Then the average value G0 of the function G(k) is
rigorously expressed by

• In several situations of physical interest, the Fourier

coefficients in expression (2.46) depend only on the
modulus |tn|; in these situations, expansion (2.46) can be
recast to the form

Chapter 2
Geometrical Description of Crystals:Direct and Reciprocal Lattices