Chapter II: Reciprocal lattice

Read chapter 2 of Kittel

 How can we study crystal structure?
• Need probe that can penetrate into crystal
• X-rays, neutrons, (high energy electrons)

• X-rays discovered by Roentgen in 1895 - instant sensation

round the world - view of his wife’s hand
• Neutrons (discovered in 1932) penetrate with almost no
interaction with most materials
 How can we study crystal structure?
• X-rays scatter from the electrons - intensity proportional to
the density n(r) - Mainly the core electrons around the
nucleus
• Similarly for high energy electrons
• Neutrons scatter from the nuclei
(and electron magnetic moment)

• In all cases the scattering is periodic - the same in each cell

of the crystal
• Diffraction is the constructive interference of the scattering
from the very large number of cells of the crystal
The crystal can be viewed as made up
of planes in different ways
Lattice

(01)
a2
φ
a1
(14)

• Low index planes: more lattice points, more widely

spaced
• High index planes: less lattice points, more closely
spaced
• Bragg model: incident waves are reflected specularly
from parallel planes
 Bragg Scattering Law
λ

θ θ
d

d sin θ
• Condition for constructive interference:
2d sin θ = n λ
• Maximum λ = 2d
• Thus only waves with λ of order atomic size can
have Bragg scattering from a crystal
 Single crystal diffraction

Rotate both sample and

detector about axis

2θ

• Crystal must be oriented in all directions

in 3D space using “Gonier Spectrometer”

• Observe scattering only at Bragg angles for a fixed

wavelength x-ray or neutrons or …..
 Alternative approach -
energy dispersive diffraction
Experiment

Photons with
electrons selected
energy

Single crystal
Photons - broad monochrometer
range of energies

•For fixed angle θ , vary the energy (i.e., λ) to satisfy Bragg condition

•X-rays over broad energy range now available at synchrotrons

•Diffraction (Bragg scattering) from a single crystallite used to

select X-rays with desired wavelength
 Scattered wave amplitude

• The Bragg law gives the condition for the constructive

interference of waves scattered from lattice planes.

• We need a deeper analysis to determine the scattering

intensity from the basis of atoms, i.e. from the spatial
distribution of electrons within each cell.

• We will use the periodicity of the electron number density

n(r) to perform Fourier analysis.

• We end up with a second lattice associated with the

crystal – reciprocal lattice
Periodic Functions and Fourier Analysis
• Any periodic function can be expressed in terms of its
periodic Fourier components (harmonics).
• Example of density n(x) in 1D crystal:

n(x) = n0 + Σp>0[Cp cos (2π p x/a) + Sp sin (2π p x/a) ]

• Easier expression:
n(x) = Σp npexp( i 2π p x/a)

(easier because exp( a + b) = exp( a ) exp( b) )

• Expression for Fourier Components:

np = a-1 ∫0a dx n(x) exp( - i 2π p x/a)
 Periodic functions and Fourier Analysis
• Define vector position r = (x,y) (2D), r = (x,y,z) (3D).
• Fourier analysis
f(r) = ΣG fG exp( i G ⋅ r)
where the G’s are vectors, i.e.,
exp( i G ⋅ r) = exp( i (Gx x + Gy y + Gz z) )

• A periodic function satisfies

f(r) = f(r + T) where T is any translation
T(n1,n2,…) = n1 a1 + n2 a2 (+ n3 a3 in 3D),
where the n’s are integers
• Thus
f(r + T) = ΣG fG exp( i G . r) exp( i G ⋅ T) = f( r )
⇒ exp( i G ⋅ T) = 1 ⇒ G ⋅ T = 2π x integer
 Reciprocal Lattice
• The reciprocal lattice is the set of vectors G in Fourier space
that satisfy the requirement
G ⋅ T = 2π x integer for any translation
T(n1,n2,…) = n1 a1 + n2 a2 (+ n3 a3 in 3D)

• How to find the G’s ??

• Define vectors bi by
bi ⋅ aj = 2π δij , where δii = 1, δij = 0 if i ≠ j

• If we define the vectors

G(m1,m2,…) = m1 b1 + m2 b2 (+ m3 b3 in 3D),
where the m’s are integers, then clearly
G ⋅ T = 2π x integer for any T
 Reciprocal Lattice and Translations
• Note: Reciprocal lattice is defined only by the vectors
G(m1,m2,…) = m1 b1 + m2 b2 (+ m3 b3 in 3D),
where the m’s are integers and
bi ⋅ aj = 2π δij , where δii = 1, δij = 0 if i ≠ j

• The only information about the actual basis of atoms is in the

quantitative values of the Fourier components fG in the
Fourier analysis
f(r) = ΣG fG exp( i G ⋅ r)

• Inversion:
fG = Vcell-1∫cell dr f(r) exp(- i G ⋅ r)
 Reciprocal Lattice and
Fourier Analysis in 1D
• In 1D, b = 2 π /a, b and a parallel
• Periodic function f(x):

f(x) = Σp fp exp( i 2π p x/a)

= Σp fp exp( i p b), p = integer

• The set of all integers x b are the reciprocal lattice

a

b
 Real & Reciprocal lattices in 2 D

a2 b2

b2 a2
a1
b1
a1
Wigner-Seitz Cell
b1
Brillouin Zone

• Two lattices associated with crystal lattice

• b1 perpendicular to a2 , b2 perpendicular to a1
• Wigner-Seitz cell of reciprocal lattice called the “First
Brillouin Zone” or just “Brillouin Zone”
Ex. What is the relationship between b1 and b2, if a1>a2?
 Reciprocal Lattice in 3D

• The primitive vectors of the reciprocal lattice are defined

by the vectors bi that satisfy
bi ⋅ aj = 2π δij , where δii = 1, δij = 0 if i ≠ j

• How to find the b’s?

• Note: b1 is orthogonal to a2 and a3, etc.

• In 3D, this is found by noting that (a2 x a3 ) is orthogonal
to a2 and a3
• Also volume of primitive cell V = |a1 ⋅ (a2 x a3 )|
• Then bi = (2π / V ) (aj x ak ),
where (i, j, k) = (1,2,3), (2,3,1) or (3,1,2)
 a1 = x̂ / 2 − ŷ / 2 + ẑ / 2
a 2 = x̂ / 2 + ŷ / 2 − ẑ / 2
a 3 = − x̂ / 2 + ŷ / 2 + ẑ / 2

2π
bi = a j × ak
V

Ex. Write the primitive vectors

of the reciprocal lattice in terms
of xˆ , ˆy, ˆz
 Real and reciprocal lattice
(recall Bravais exercises)

• the reciprocal vector G= h b1 + k b2 + l b3 is

perpendicular to the real lattice plane with index
(h k l)

• the distance between two consecutive (h k l)

planes is 2π
d hkl = n
G

• See also Problem 2.1 in Kittel

 Scattering and Fourier Analysis
λ
kout
kin

θ
d

• The in and out waves have the form:

exp( i kin. r - i ωt) and exp( i kout. r - i ωt)
• If the in wave drives the electron density, which
then radiates waves, the outgoing amplitude is
proportional to:
F= ∫space dr n(r) exp(i (kin - kout )⋅ r)
 Scattering and Fourier Analysis
λ
kout
kin ∆k = G

θ
d
• Define ∆k = kout - kint
• Then we know from Fourier analysis that
F = ∫space dr n(r) exp(- i ∆k . r) = N cell V cell nG
only if ∆k = G, where G = recip. lat. vector
• Otherwise integral vanishes ⇒ no diffraction
• nG = V cell-1∫cell dr n(r) exp(- i G ⋅ r)

The set of reciprocal lattice vectors determines the

possible x-ray reflections
 Elastic Scattering
λ
kout
kin ∆k = G

θ
d

• For elastic scattering (energy the same for in and

out waves)
| kin | = | kout |, or kin2 = kout2 = ( kin + G)2
• Then one arrives at the condition for diffraction:
2 | kin. G | = G2
 Ewald Construction

• Laue equations:

kout
a1 • ∆k = 2πh
G
a 2 • ∆k = 2πk kin
2θ 90º−θ
a 3 • ∆k = 2πl

kout = kin + G
| 2 kin⋅ G | =2 | kin | | G | cos (90º + θ)= 2 | kin | | G | sin θ
 Equivalent to
Bragg Condition

kout
G
kin
2θ
• From last slide,
since G2 = | G |2 :

| G | = 2 | kin | sin θ
• But | kin | = 2π/λ, and | G | = n (2π/d), where d =
spacing between planes (see Kittel prob. 2.1)
• ⇒ Bragg condition 2d sin θ = n λ
 Geometric Construction of
Diffraction Conditions
b2
• Consequence of condition G
| 2 kin ⋅ G | = G2
kin
• | kin ⋅ G/2 | = (G/2)2
• The vector kin (also kout) lies b1
along the perpendicular bisecting
plane of a G vector kout
• One example is shown
 Diffraction and the
Brillouin Zone
b2
G
• Brillouin Zone formed by kin
perpendicular bisectors
of G vectors b1

kout
• Consequence: Brillouin Zone
No diffraction for any k
inside the first Brillouin Zone
• Special role of Brillouin Zone (Wigner-Seitz cell
of reciprocal lattice) as opposed to any other
primitive cell
 Comparison of diffraction
from different lattices

• The Bragg condition can also be written

| G | = 2 | kin | sin θ
⇒ sin θ = (λ /4π) | G |
• Thus the ratios of the sines of the angles for
diffraction are given by:
sin θ1 / sin θ2 = | G1 | / | G2 |
• Each type of lattice has characteristic ratios
the positions of diffraction peaks as a function of
sin θ
• Simple scaling with λ
 Experimental Powder Pattern
http://www.uni-wuerzburg.de/mineralogie/crystal/teaching/teaching.html

• Diffraction peaks at angles satisfying the Bragg

condition

Differences for
imperfect powder
averages

Reciprocal Lattice units

 Fourier analysis of the basis
• The intensity of the diffraction at each G is
proportional to the square of the scattering
amplitude
F = N ∫cell dr n(r) exp(- i G . r)= NSG
• SG – structure factor
• Regard the crystal density n(r) as a sum of atomic-
like densities natom (r - Ri), centered at point Ri
n(r) = ∑ all i natom i ( r - Ri)
• Then also
SG = ∑ i in cell ∫space dr natom i (r - Ri) exp(- i G ⋅r)
Cell
One atom per cell and Form Factor
• Then one can set Ri = 0 and SG is the Fourier
transform of one atom density
f = ∫space dr natom (r) exp(- i G ⋅ r)

natom (r) |r|

• Called Form Factor

• In the limit of point-like atoms f=Z

f Values of |G| for a

particular crystal

|G|
 More than one atom per cell

• SG = ∑ i in cell ∫space dr natom i ( r - Ri) exp(- i G ⋅ r)

= ∑ i in cell exp(- i G ⋅ Ri)

∫space dr natom i ( r - Ri) exp(- i G ⋅ (r - Ri) )

= ∑ i in cell exp(- i G ⋅ Ri)

∫space dr natom i ( r) exp(- i G ⋅ r)

= ∑ i in cell exp(- i G ⋅ Ri) fG atom i

• Interpretation: Form factor fG atom i and phase factor

exp(- i G . Ri) for each atom in unit cell
 Structure factor and atomic form factor
• The amplitude of the scattered electromagnetic wave is
FG = NS G
• The structure factor of the base is
SG = ∑
i in cell
f Gatom i exp( −iG ⋅ Ri )

• The atomic form factor

fj = f = ∫ dV n ( r ) exp( −iG ⋅ r )
atom j
G j
unit cell
 “Pure” Structure factor

• Often the basis contains more than one atom that is

same element, e.g., diamond structure

• Then fG atom i = fG atom is the same and

SG = ∑ i in cell exp(- i G ⋅ Ri) SG atom i
= fG atom ∑ i in cell exp(- i G ⋅ Ri)

• Define “pure” structure factor

S0G = (1/n) ∑ i in cell exp(- i G ⋅ Ri)

where n = number of atoms in cell

• Then SG = n S0G fG atom

 Body Centered Cubic viewed as
Simple Cubic with 2 points per cell

S0G = (1/2) ∑ i =1,2 exp(- i G ⋅ Ri)

= (1/2) ( 1 + exp(- i G ⋅ R2)
= (1/2) exp(- i G ⋅ R2/2) a3
[exp( i G ⋅ R2/2) + exp(- i G ⋅ R2/2) ]
= exp(- i G ⋅ R2/2) cos ( G ⋅ R2/2)
a2
Result: If G = (v1 v2 v3) 2π/a
|S0G | = 1 if sum of integers a1
is even a
| S0G | = 0 if sum is odd
Points at
Same as we found before! R1 = (0,0,0)
FCC reciprocal lattice R2 = (1,1,1) a/2
 Face Centered Cubic viewed as
Simple Cubic with 4 points per cell
S0G = (1/4) ∑ i =1,4 exp(- i G . Ri)

Result:
a3
If G = (v1 v2 v3) 2π/a
then

S0G = 1 if all integers

are odd or all are even a2

a1
S0G = 0 otherwise a

Same as we found before! Points at (0,0,0) ; (1,1,0) a/2 ;

BCC reciprocal lattice (1,0,1) a/2 ; (0,1,1) a/2
 Structure factor for diamond

• Ex: diamond structure

S0G = (1/2) ∑ i =1,2 exp(- i G . Ri)

• R1 = + (1/8, 1/8, 1/8)a

R2 = - (1/8, 1/8, 1/8)a