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One can go from any location in the lattice to an identical location by
following path composed of integer multiples of the vectors a and b .
NOTE: Keep in mind that basic building blocks of periodic structures can be more
complicated than a single atom: e.g., in NaCl, the basic building block is composed of one
Na and one Cl ion which is repeated in a cubic pattern to make the NaCl crystalline
structure.
SPACE GROUP: The complete set of rigid body motions that take
crystal into itself
S = t + R ( uˆ , θ )
PHYS 624: Crystalline Solids: Symmetry and Bonding
5 Bravais Lattices in 2D
Wigner-Seitz cell
Inversion Symmetry is
obeyed by all lattices:
Invariance under
r → −r
2D lattices are not mathematical fiction→they naturally appear as surfaces
and interfaces of real crystals.
PHYS 624: Crystalline Solids: Symmetry and Bonding
Bravais Lattice, Primitive Vectors,
and Unit Cells
A collection of points in which the neighborhood of each point is the
same as the neighborhood of every other point under some translation is
called a Bravais lattice.
The primitive unit cell is the parallel piped (in 3D) formed by the
that
primitive lattice vectors which are defined as those lattice vectors
produce the primitive cell with the smallest volume Ω = a × (b ⋅ c )
P
Non-primitive unit cell: Lattice region (which can contain several sites
and usually has the same Point Group symmetry as the lattice itself) which
produces the full crystal upon repetition.
Start with
hexagonal 2D
lattice (A) and
replace single
point in the center
with a pair of
points (B).
The dotted line is a glide line the lattice is invariant when translated
vertically by a/2 and reflected about this line, but it is not invariant
under either operation separately!
PHYS 624: Crystalline Solids: Symmetry and Bonding
Non-Primitive Unit Cell
Non-Primitive (Elementary) Unit Cell: Minimal volume of the crystal
(containing several particles) which has the same point group symmetry
as the crystal itself and which produces the full crystal upon repetition.
i
rn = Rn + ri
ri = xa
i 1 + yi a2 + zi a3
xi , yi , zi ∈(0,1), i =1,2,…, k
In deforming the
rectangular
lattice into the
centered
rectangular
lattice, reflection
symmetry about
the y axis is
destroyed.
Two lattices are equivalent if their space groups S and S’ are the same up to
linear change of coordinate systems (i.e., there exist a single matrix O
representing the change of coordinate system):
ORO −1
+O −1
t = R ′ + t′
PHYS 624: Crystalline Solids: Symmetry and Bonding
17 Distinct 2D Lattices
The various planar patterns can by classified by the transformation
groups that leave them invariant, their symmetry groups. A mathematical
analysis of these groups shows that there are exactly 17 different plane
symmetry groups:
http://www.clarku.edu/~djoyce/wallpaper/seventeen.htm
PHYS 624: Crystalline Solids: Symmetry and Bonding
14 Bravais Lattices and
7 Crystal Systems in 3D
ΩC
Ω PUC =
2
ΩC
Ω PUC =
2
ΩC
Ω PUC =
4
Stereogram: Two-dimensional
projections of a point (that does not
belong to any special axis or plane of
symmetry) on the surface of a sphere
and its images generated by acting on
the sphere with various symmetry
operations of the point group. Pick a
point on a sphere
PHYS 624: Crystalline Solids: Symmetry and Bonding
230 Space Groups:
Symmorphic vs. Non-Symmorphics
The space group always has only translations as its subgroup
T = {E, Rn} < S
In general, it cannot be formed from these subgroups because of the glide
planes (translation + reflection) and screw axes (translation + rotation).
{R | t } ∈ S; t ≠ 0,{E | t } ∉T ⇒ S ≠ P ×T
t
In general, Point Group leaves the Bravais lattice invariant but not
the crystal itself (recall that the crystal is defined as the Bravais
lattice and the atomic basis in each unit cell).
157 Non-Symmorphic Groups: include glyde planes and screw axes.
73 Symmorfic Groups: P < S , S = P ∧ T
1651 Magnetic (Shubnikov or Color) Groups: for the lattices whose
points are decorated with quantum-mechanical spin-½.
PHYS 624: Crystalline Solids: Symmetry and Bonding
Classical Consequences of Symmetry
Sharp peaks in X-ray diffraction pattern are exclusively result of
lattice symmetries (the intensity of the peaks depends on details).
UHU = Hˆ ⇒ [ Hˆ , Uˆ ] = 0
ˆ ˆ ˆ †
Uˆ u j = u j u j ⇒ Iˆ = ∑ j
u j u j
∑k
ui Uˆ uk uk Hˆ u j = ∑ ui Hˆ uk uk Uˆ u j ≡ 0
k
⇕
( u Uˆ u
i i − u j Uˆ u j )u i Hˆ u j = 0 ↔ (ui − u j ) ui Hˆ u j = 0
PHYS 624: Crystalline Solids: Symmetry and Bonding
Quantum Consequences of Symmetry:
Band Structure and Selection Rules
Effective single-particle Hamiltonian of a solid commutes
with the representations of space group operations:
n n
[ H ,U{U |t} ] = 0 ⇒ U{U |t}[ H Ψk (r )] = U{U |t}[ε n (k )Ψk (r )]
ˆ ˆ
⇓ n
H[U{U |t}Ψk (r )] = ε n (k )[U{U |t}Ψk (r )]
ˆ ˆ n ˆ
One can further reduce complexity from solving Schrödinger equation
in a unit cell (secured by translational symmetry) to finding band
dispersion and Bloch eigenstates only in a portion of the BZ.
ε n (Uk ) = ε n (k )
{U | t }∈ S ⇒ n n −1 −1
ΨUk (r ) = U{U |t}Ψk (r ) = Ψk (U r −U t )
ˆ n
Valance orbitals, which generally have a greater spatial extent, will overlap
more so their bands will broaden more.
Eventually we will stop gaining energy from bringing the atoms closer
together, due to overlap of the cores ⇒ Once we have reached the optimal point
we fill the states 2 particles per, until we run out of electrons.
Electronic correlations n↑ n↓ complicate this simple picture of band
formation since they strive to keep the orbitals from being multiply occupied.
l (l + 1) 2ℏ2n2
V (r ) + C 2
⇒ Z → Znl
r
Level crossings due to atomic screening. The potential felt by states with large l are
screened since they cannot access the nucleus. Thus, orbitals of different principle
quantum numbers can be close in energy. For example, in elemental Ce (4f15d16s2) both
the 5d and 4f orbitals may be considered to be in the valence shell, and form metallic
bands. However, the 5d orbitals are much larger and of higher symmetry than the 4f
ones. Thus, electrons tend to hybridize (move on or off) with the 5d orbitals more
effectively. The Coulomb repulsion between electrons on the same 4f orbital will be
strong, so these electrons on these orbitals tend to form magnetic moments.
Lowering of zero-point
energy by dipole-dipole
interaction:
2
ℏω0 2e ℏ → 0
2
∆E ≈ 2 3 → 0
4 mω0 R
PHYS 624: Crystalline Solids: Symmetry and Bonding
Chemical Bonds in Solids: Covalent
e ±1 B 1
The energy per molecule of a crystal of Φ = N pairs −
4πε 0 r ∑ + n
pij r
∑ pijn
sodium chloride is (7.9-5.1+3.6) eV=6.4eV
i≠ j i≠ j
lower than the energy of the separated
neutral atoms. The cohesive energy with
respect to separated ions is 7.9eV per Coulomb
molecular unit. All values on the figure
Repulsion between
are experimental. Madelung constant (A=1.748 for NaCl) electron clouds
PHYS 624: Crystalline Solids: Symmetry and Bonding
Covalent vs. Ionic Bonding:
Valence Charge Density
Ionic and covalent bondings are two limiting cases, of which, only the later
can exist in solids composed of a single type of atom. In majority of cases the
bonding is of an intermediate nature representing a mixture of the two
extremes.
In metallic Ni (FCC, 3d84s2), the 4s- and 3d-orbitals are almost degenerate
and thus, both participate in the bonding. However, the 4s-orbitals are so large
compared to the 3d-orbitals that they encompass many other lattice sites,
forming non-directional bonds. In addition, they hybridize weakly with the d-
orbitals (the different symmetries of the orbitals causes their overlap to
almost cancel) which in turn hybridize weakly with each other. Thus, whereas
the s-orbitals form a broad metallic band, the d-orbitals form a narrow one.
Hydrogen bond
Covalent bond
2mi =1
Virial Theorem: Telectron = − E − ∑ rknucl ⋅ ∇ nk E
N
N
nucl n
k =1 V = 2 E + ∑ rk ⋅ ∇ k E
k =1
nucl nucl
Stability: E0 < E∞ , ∇ k E (r1 ,… rN ) 0 = 0
n
= (φ i + φ i ) , Ψ i = (φ i − φ i B )
1 A 1 A
Ψ b(onding)
i
B a(ntibonding)
2 2
PHYS 624: Crystalline Solids: Symmetry and Bonding
Diamond vs. Graphite: Insulator vs. Semimetal
1 A, B 2 A, B
φ1A,B = s ± px
3 3
1 A, B 1 A, B 1 A, B
φ2A, B = s ∓ px ± py
3 6 2
1 A, B 1 A, B 1 A, B
φ3A, B = s ± px ± py
3 6 2
φ4A, B = pzA,B
ε s + 2ε p
3
= (φ i + φ i ) , Ψ i = (φ i − φ i B )
1 A 1 A
Ψ b(onding)
i
B a(ntibonding)
2 2
PHYS 624: Crystalline Solids: Symmetry and Bonding
Crystalline Phases of Carbon:
Carbon Nanotubes
(8, 4) (7, 0) (4, 4)