Homework #4

1. It is often convenient to represent a fcc lattice as simple cubic, with a cubic primitive
cell of side a and a four-point basis.
(a) Show that the structural factor is then either 4 or 0 at all points of the simple cubic
reciprocal lattice.
(b) Show that when points with zero structural factor are removed, the remaining
points of the reciprocal lattice makes up a bcc cubic lattice with conventional cell of
side 4/a. Why is this expected?

Solution:
(a)
r r r
a1 = ax , a 2 = ay , a3 = az .
r 2 r 2 r 2
b1 = x , b2 = y , b3 = z .
a a a
There are four lattice sites within each cubic cell.
r r a r a r a
R1 = 0, R2 = ( x + y ), R3 = ( y + z ), R4 = ( z + x ) .
2 2 2
4 r r
The structure factor is S = exp(iG Ri )
i =1
r r r r 2
with G = hb1 + kb2 + lb3 = (hx + ky + lz ) .
a
r r
G R1 = 0
r r
G R2 = ( h + k )
r r
G R3 = ( k + l )
r r
G R4 = (l + h )
4 r r
S = exp(iG Ri ) = 1 + exp[i ( h + k )] + exp[i ( k + l )] + exp[i (l + h )] .
i =1

S = 4 when h, k , l are all even or all odd.

S = 0 otherwise.

r r r r 2
(b) Keep only those sites of G = hb1 + kb2 + lb3 = (hx + ky + lz ) with all even or all
a
odd h, k , l , such as (000), (200), (111), (002), , plot the reciprocal lattice.
 z
(002) (022)

(202) (222)
(111)
(000) (020) y

(200)
(220)

x 2
a
This is a bcc lattice with a lattice constant of 4 / a . This is expected because the
reciprocal lattice of a fcc should be a bcc lattice.

2. Structure factor of diamond. The crystal structure of diamond is described in

Chapter 1. The basis consists of eight atoms if the cell is taken as the conventional
cube. (a) Find the structural factor S of this basis. (b). Find the zeros of S and show
that the allowed reflections of the diamond structure satisfy v1 + v2 + v3 = 4n , where
all indices are even and n is any integer, or else all indices are odd (Notice that h, k, l
may be written for v1 , v2 , v3 and this is often done.)

Solution:
8 r r
(a) S = exp(iG Ri )
i =1
r r r r r r r r
R1 , R2 , R3 , R4 are the four atoms in a fcc cubic cell. R5 , R6 , R7 , R8 are the four atoms
r
in another fcc cubic cell which is shifted by R0 = ( x + y + z )a / 4 . Thus
r r r r r r r r r r r r
R5 = R1 + R0 , R6 = R2 + R0 , R7 = R3 + R0 , and R8 = R4 + R0 .
8 r r 4 r r 4 r r r
S = exp(iG Ri ) = exp(iG Ri ) + exp[iG ( Ri + R0 )]
i =1 i =1 i =1
r r 4 r r
= [1 + exp(iG R0 )] exp(iG Ri )
i =1
4 r r
The exp(iG Ri ) is the fcc structure factor.
i =1
 r r r r 2 r r
For G = hb1 + kb2 + lb3 = ( hx + ky + lz ) , G R0 = ( h + k + l ) / 4 .
a
S = {1 + exp[ ( h + k + l ) / 2)]}{1 + exp[i (h + k )] + exp[i (k + l )] + exp[i (l + h )]}

(b) The zero of S occurs when h, k , l are not all even or odd due to the fcc
structure factor, or when h + k + l = 4n + 2 (n=integer) that gives
1 + exp[ ( h + k + l ) / 2) = 0 .
When h + k + l = 4n and all h, k , l are even, S = 8 .
When h + k + l = 4n 1 and all h, k , l are odd, S = 4(1 i ) .

3. Diatomic line. Consider a line of atoms ABAB..AB, with A-B bond length of a/2.
The form factors are fA and fB for atoms A, B, respectively. The incident beam of x-
rays is perpendicular to the line of atoms. (a) Show that the interference condition is
n = a cos , where is the angle between the diffraction beam and the line of
atoms. (b) Show that the intensity of the diffracted beam is proportional to
| f A f B |2 for n odd, and to | f A + f B |2 for n even. (c) Explain what happens if
f A = fB .

Solution:

a l

A B A B A B A B A B
r 2n
The reciprocal lattice vector is G = x with n being integers.
a
r r a
Within a cell, R A = 0, RB = x . Then the structure factor is
2
r r f f B n = odd
S = f A + f B exp(iG RB ) = f A + f B exp(in ) = A .
f A + f B n = even
(a) The path difference is l = a cos so the interference condition is a cos = .
| f f B |2 n = odd
(b) I | S |2 = A .
A
| f + f B |2
n = even
(c) If f A = f B , I =0 when n is odd. In this case, the lattice is a monatomic lattice
with lattice constant of a/2. The reciprocal lattice is 2m /(a / 2) = ( 2 / a )2m .
Thus only n = 2m = even gives the diffraction.
4. Powder specimens of three different monoatomic cubic crystals are analyzed with a
Debye-Scherrer camera. It is known that one sample is fcc, one is bcc, and one has
the diamond structure. The approximate positions of the first four diffraction rings in
each case are:
A B C
42.2 o 28.8o 42.8o
49.2o 41.0o 73.2o
72.2 o 50.8o 89.0o
87.3o 59.6o 115.0o
(a) Identify the crystal structures of A, B, and C.
(b) If the wavelength of the incident x-ray beam is 1.5, what is the length of the side
of the conventional cubic cell in each case?

Sample
Film
Solution:
The Bragg law gives 2d sin = . For this problem, = / 2 .
r
|G |
sin( / 2) = = = h2 + k 2 + l 2 .
2d 2 2 2a

For fcc lattice, h, k , l need to be all even or all odd. The first four diffraction
peaks then correspond to (111), (200), (220), and (311) which give

sin(1 / 2) = 3 , sin( 2 / 2) = 2 , sin( 3 / 2) = 2 2 , sin( 4 / 2) =
11 .
2a 2a 2a 2a
sin( 2 / 2) 2 sin(3 / 2) 2 2 sin( 4 / 2) 11
or = = 1.155, = = 1.633, = = 1.915.
sin(1 / 2) 3 sin(1 / 2) 3 sin(1 / 2) 3

For bcc lattice, h + k + l needs to be even. The first four diffraction peaks then
correspond to (110), (200), (112), and (220) which give

sin(1 / 2) = 2 , sin( 2 / 2) = 2 , sin(3 / 2) = 6 , sin( 4 / 2) = 8.
2a 2a 2a 2a
sin( 2 / 2) 2 sin(3 / 2) 6 sin( 4 / 2) 8
or = = 1.414, = = 1.732, = = 2.
sin(1 / 2) 2 sin(1 / 2) 2 sin(1 / 2) 2
For diamond structure, h, k , l need to be all even or all odd plus
1 + exp[ ( h + k + l ) / 2) 0 . The first four diffraction peaks then correspond to (110),
(220), (311), (400) which give

sin(1 / 2) = 3 , sin( 2 / 2) = 8 , sin(3 / 2) = 11 , sin( 4 / 2) =
4.
2a 2a 2a 2a
sin( 2 / 2) 8 sin(3 / 2) 11 sin( 4 / 2) 4
or = = 1.633, = = 1.915, = = 2.309.
sin(1 / 2) 3 sin(1 / 2) 3 sin(1 / 2) 3

A sin (i / 2 ) sin(i / 2)
sin(1 / 2)
42.2 0 0.3616
49.2 0 0.4163 1.15
72.2 0 0.5892 1.63
87.30 0.6903 1.91

B sin (i / 2 ) sin(i / 2)
sin(1 / 2)
28.80 0.2487
41.00 0.3502 1.41
50.80 0.4289 1.72
59.60 0.4970 2.00

C sin (i / 2 ) sin(i / 2)
sin(1 / 2)
42.80 0.3616
73.2 0 0.4163 1.63
89.0 0 0.5892 1.92
115.00 0.6903 2.31

Comparing to the calculated ratio, it is easy to see A is fcc, B is bcc, and C has
diamond structure.

3 1.5 3 0
(b) For A, sin(1 / 2) = 3. a = = = 3.59 A .
2a 2 sin(1 / 2) 2 0.3616
2 1.5 2 0
For B, sin(1 / 2) = 2. a= = = 4.26 A
2a 2 sin(1 / 2) 2 0.2487
3 1.5 3 0
For C, sin(1 / 2) = 3. a= = = 3.56 A
2a 2 sin(1 / 2) 2 0.3649