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Lecture Notes-19

NOTES

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Lecture Notes-19

NOTES

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Talha Ejaz

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Please note that this was my last lecture on X-Ray Diffraction

(Dr. Syed Rizwan Ali)

Geometrical Interpretation: Laue Conditions

 To obtain an elastic diffraction peak: 𝑮(= 𝒌′ − 𝒌)

must satisfy the Laue conditions and 𝒌′ = 𝒌 ,
∆𝒌. 𝒂𝟏 = 2ℎ𝜋 ∆𝒌. 𝒂𝟐 = 2𝑘𝜋 ∆𝒌. 𝒂𝟑 = 2𝑙𝜋
 The first equation tells us that ∆𝒌 lies on a certain
cone about the direction of 𝒂𝟏 .
 The second equation tells us that ∆𝒌 lies on a cone
about 𝒂𝟐 .
 The third equation requires that ∆𝒌 lies on cone
about 𝒂𝟑 .
Thus, at a reflection k must satisfy all the three
equations; it must lie on a common line of
intersection of three cones.

1
Diffraction occurs when the two equations are simultaneously
satisfied, i.e., when the angles 𝜽1 and 𝜽2 define the same direction.

 Thus, at a reflection k must satisfy all the 3 equations; it

must lie on a common line of intersection of 3 cones.
 A severe condition that can be satisfied only by systematic
sweeping or searching in wavelength or crystal orientation.

2
 Laue condition severely limit the number of elastic
scattering peaks obtained for a fixed wavelength,
incident direction and crystal orientation.

 To produce elastic peaks, the crystal must be rotated

or the wavelength must be changed.

Ewald Construction
 Laue condition is a severe condition that can be satisfy only by
systematic sweeping or searching in wavelength or crystal
orientation or by sheer accident.
 A beautiful construction , the Ewald construction can be used to
visualize the nature of the accident that must be occur in order to
satisfy the diffraction conditions in three dimensions.
 This is a geometric construction used in electron, neutron, and X-
ray crystallography. It demonstrates the relationship between:
 the wavevector of the incident and diffracted x-ray beams,
 the diffraction angle for a given reflection,
 the reciprocal lattice of the crystal

 Ewald's sphere can be used to find the maximum

resolution available for a given x-ray wavelength and the unit cell
dimensions. It is often simplified to the two-dimensional "Ewald's
circle" model

3
 Reciprocal lattice points are drawn with positions:
𝑮 = 𝒉𝑨𝟏 + 𝒌𝑨𝟐 + 𝒍𝑨𝟑 .
 The propagation vector 𝒌 for the incident wave is
drawn with its head at any one of the points.

 A sphere with radius 𝒌 = 𝟐𝝅/𝞴 is drawn centered at

the tail of 𝒌.
 A diffracted beam will be formed if the surface of the
sphere passes through another reciprocal lattice
point.

4
 A sphere as drawn here intercepts a reciprocal lattice
point thus:
𝒌′ = 𝒌 + 𝑮
 Here 𝜽 is the Bragg angle

Calculations for the structure factor

Recall Eq. [14]; 𝑭= 𝒇𝒎 𝒆−𝒊 ∆𝒌 . 𝒑𝒎 structure factor
𝒎
is called the structure factor (or more precisely structure
factor of the basis) and gives the sum of all the waves
scattered from electrons in a single unit cell, apart from
the amplitude factor A.

𝑭= 𝒇𝒎 𝒆−𝒊 𝑮 . 𝒑𝒎
𝒎
Sum is over all atoms of the basis

Let us generalize the formula and apply it to different

lattices

5
Let the basis vector is given by;
𝒑𝒎 = 𝒙𝒋 𝒂𝟏 + 𝒚𝒋 𝒂𝟐 + 𝒛𝒋 𝒂𝟑
Then, for a reflection labelled by 𝒉, 𝒌, 𝒍 we have;
𝑮 = 𝒉𝑨𝟏 + 𝒌𝑨𝟐 + 𝒍𝑨𝟑 .
 𝑮. 𝒑𝒎 = 𝟐𝝅 (𝒙𝒋 𝒉 + 𝒚𝒋 𝒌 + 𝒛𝒋 𝒍). unit cell volume 𝝉 = 𝟏

The structure factor becomes; also; 𝑮 = ∆𝒌

Atomic positions
−𝟐𝝅𝒊 (𝒙𝒋 𝒉+𝒚𝒋 𝒌+𝒛𝒋 𝒍) within the unit cell
𝑭= 𝒇𝒎 𝒆
𝒎
Sum is over all atoms of the basis whose positions are
given by (𝒙𝒋 , 𝒚𝒋 , 𝒛𝒋 )

DIGRESSION
𝒆−𝒊𝜽 = 𝒄𝒐𝒔 𝜽 − 𝒊 𝒔𝒊𝒏 𝜽 𝒆 𝒊𝜽 = 𝒄𝒐𝒔 𝜽 + 𝒊 𝒔𝒊𝒏 𝜽
𝒆−𝒊𝒏𝝅 = 𝒄𝒐𝒔 𝒏𝝅 − 𝒊 𝒔𝒊𝒏(𝒏𝝅)
𝒆−𝒊𝒏𝝅 = 𝒄𝒐𝒔 𝒏𝝅 𝑩𝒆𝒄𝒂𝒖𝒔𝒆: 𝒔𝒊𝒏 𝒏𝝅 = 𝟎
When n is even.
𝒆−𝒊𝒏𝝅 = 𝒄𝒐𝒔 𝒆𝒗𝒆𝒏 × 𝝅 = +𝟏
 𝒆−𝒊𝝅×(𝒐𝒅𝒅 𝒊𝒏𝒕𝒆𝒈𝒆𝒓) = −𝟏
When n is odd.
𝒆−𝒊𝒏𝝅 = 𝒄𝒐𝒔 𝑶𝒅𝒅 × 𝝅 = −𝟏

 𝒆−𝒊𝝅×(𝒆𝒗𝒆𝒏 𝒊𝒏𝒕𝒆𝒈𝒆𝒓) = +𝟏

6
Calculate the structure factor for bcc lattice
The bcc basis has two identical atoms: (𝒇𝒎 ≡ 𝒇)
1 1 1
(𝑥1 , 𝑦1 , 𝑧1 ) ≡ (0,0,0) and (𝑥2 , 𝑦2 , 𝑧2 ) ≡ (2 , 2 , 2)

𝑭= 𝒇𝒎 𝒆−𝟐𝝅𝒊 (𝒙𝒋 𝒉+𝒚𝒋𝒌+𝒛𝒋 𝒍)

𝒎
𝟏 𝟏 𝟏
𝑭 = 𝒇 [𝒆−𝟐𝝅𝒊 (𝟎𝒉+𝟎𝒌+𝟎𝒍) + 𝒆−𝟐𝝅𝒊 (𝟐𝒉+𝟐𝒌+𝟐𝒍)]

𝑭 = 𝒇 [𝟏 + 𝒆−𝒊𝝅 (𝒉+𝒌+𝒍) ]
Where 𝒇 is the form factor of an atom.
The value of F is zero whenever the exponential has
the value -1. This will occur whenever the argument
is −𝒊𝝅 × (𝒐𝒅𝒅 𝒊𝒏𝒕𝒆𝒈𝒆𝒓). Thus we have,

𝑭 = 𝒇 [𝟏 + 𝒆−𝒊𝝅 (𝒉+𝒌+𝒍) ]
 𝒆−𝒊𝝅×(𝒐𝒅𝒅 𝒊𝒏𝒕𝒆𝒈𝒆𝒓) = −𝟏  𝒆−𝒊𝝅×(𝒆𝒗𝒆𝒏 𝒊𝒏𝒕𝒆𝒈𝒆𝒓) = +𝟏

𝑭 = 𝟎 when 𝒉 + 𝒌 + 𝒍 = 𝒐𝒅𝒅 𝒊𝒏𝒕𝒆𝒈𝒆𝒓.

𝑭 = 𝟐𝒇 when 𝒉 + 𝒌 + 𝒍 = 𝒆𝒗𝒆𝒏 𝒊𝒏𝒕𝒆𝒈𝒆𝒓.
EXAMPLE: Metallic sodium:
It has bcc structure. The diffraction pattern does not
contain lines such as (100), (300), (111), or (221), but
it contain lines such as (200), (110), and (222)

7
Explanation of the absence of a (100)
reflection from a body-centered cubic lattice.
 (100) Reflection normally occurs when reflections from
the planes that bound the cubic unit cell (i.e., (100))
differ in phase by 2𝝅.
 In a bcc lattice there is an intervening second plane (as
shown) of atoms, which is equal in scattering power to
the other planes.
 This middle plane gives a reflection retarded in phase
by 𝝅 with respect to the first plane, thereby canceling
the contribution from that plane.
 The cancellation of the (100) reflection occurs in the
bcc lattice because the planes are identical in
composition.

Physical Interpretation of systematic absences:

Example: Why (100) reflection vanishes in bcc lattice?

 Similar cancellation can be found in the hcp structure.

8
Structure factor for CsCl structure J. Richard Christman,
Fundamentals of Solid
State, John Wiley

Calculate the structure factor for fcc lattice

The bcc basis has 4 identical atoms: (𝒇𝒎 ≡ 𝒇)
𝟏 𝟏
(𝒙𝟏 , 𝒚𝟏 , 𝒛𝟏 ) ≡ (𝟎, 𝟎, 𝟎), 𝒙𝟐 , 𝒚𝟐 , 𝒛𝟐 ≡ 𝟎, 𝟐 , 𝟐 ,
𝟏 𝟏 𝟏 𝟏
(𝒙𝟑 , 𝒚𝟑 , 𝒛𝟑 ) ≡ (𝟐 , 𝟎, 𝟐), (𝒙𝟒 , 𝒚𝟒 , 𝒛𝟒 ) ≡ (𝟐 , 𝟐 , 𝟎)

𝑭= 𝒇𝒎 𝒆−𝟐𝝅𝒊 (𝒙𝒋 𝒉+𝒚𝒋𝒌+𝒛𝒋 𝒍)

𝒎
𝟏 𝟏
𝑭 = 𝒇 [𝒆−𝟐𝝅𝒊 (𝟎𝒉+𝟎𝒌+𝟎𝒍) + 𝒆−𝟐𝝅𝒊 (𝟎𝒉+𝟐𝒌+𝟐𝒍)
𝟏 𝟏 𝟏 𝟏
−𝟐𝝅𝒊 ( 𝒉+𝟎𝒌+ 𝒍) −𝟐𝝅𝒊 ( 𝒉+ 𝒌+𝟎𝒍)
+𝒆 𝟐 𝟐 +𝒆 𝟐 𝟐 ]
𝑭 = 𝒇 [𝟏 + 𝒆−𝒊𝝅 𝒌+𝒍
+ 𝒆−𝒊𝝅 𝒉+𝒍
+ 𝒆−𝒊𝝅 (𝒉+𝒌) ]
Where 𝒇 is the form factor of an atom.

9
𝑭 = 𝒇 [𝟏 + 𝒆−𝒊𝝅 𝒌+𝒍
+ 𝒆−𝒊𝝅 𝒉+𝒍
+ 𝒆−𝒊𝝅 (𝒉+𝒌) ]