Lecture 7

Crystal Geometry
and
Structure Determination

Todays lecture
Two techniques for structure determination

1. Diffractometry: Radiation of fixed

wavelength, varying angle: Park the beam
and then rotate the sample
Output: Intensity vs. angle
2. Laue reflection: Radiation of variable
wavelength, fixed angle: each wavelength
diffracts at different angle
Output: symmetry of spot pattern

How Characteristic X-rays are generated??

Characteristic X-rays
are produced by
electron transitions
between the electron
shells.
3

X-rays: Characteristic
Radiation, K
Target (Anode)
Mo
Cu
Co
Fe
Cr

Wavelength,
0.71
1.54
1.79
1.94
2.29

Note that wavelength is typically ranging between

1-2

Two things will be key to explain the

phenomenon
1. Model atoms as mirrors: Laws of specular
reflection can be applied
2. Apply interference criteria
In-phase rays-Amplify
Out of phase-Dampens

Constructive and destructive interference

In-phase (coherent) monochromatic

(single wavelength) incident radiation

X-Ray Diffraction

Bragg
Reflection

Sample

Incident Beam

Transmitted
Beam

Braggs Law (Part 1): For every diffracted beam there exists a set
of crystal lattice planes such that the diffracted beam appears to be
specularly reflected from this set of planes.

X-Ray Diffraction
Braggs Law (Part 1): the diffracted beam appears to be specularly reflected
from a set of crystal lattice planes.
Specular reflection:
Angle of incidence = Angle of reflection
(both measured from the plane and not from
the normal)

The incident beam, the reflected beam and the

plane normal lie in one plane

plane

X-Ray Diffraction

Braggs law (Part 2):

n 2d hkl sin

dhkl

dhk
l

Q
Path Difference =PQ+QR 2d hkl sin

R
Q

Path Difference =PQ+QR 2d hkl sin

Constructive inteference

n 2d hkl sin
Braggs law

A father-son team that shared a Nobel Prize

William Henry Bragg (18621942),

William Lawrence Bragg (18901971)
Nobel Prize (1915)

Interference criteria + crystal

structure = set of expected reflections
= Finger print of the crystal structure

{001} in SC reflects at {001}

However,
{001} in BCC and FCC does not
reflects at {001}

Geometric analysis of atom position yields the

following selection rules for reflection in cubic
crystals

This can be summarised in the form of extinction rule

as summarised in the next slide
Courtesy: Sadoway

Extinction Rules
Bravais Lattice

Allowed Reflections

SC
BCC
FCC

All
(h + k + l) even
h, k and l unmixed
h, k and l are all odd
Or
if all are even then
(h + k + l) divisible by 4

DC

X Ray Diffractometer

Output

You do not get indices of plane!!

Diffraction analysis of cubic

crystals
Braggs Law:

2d hkl sin

(1)

Cubic crystals

d hkl

(2)

a
h2 k 2 l 2

2
(2) in (1) => sin

2
4a 2

(h 2 k 2 l 2 )
constant

sin2 (h2 k2 l2 )

Example problem

Solving X-Ray pattern

Cu target, Wavelength = 1.5418 Angstrom
2
44.48
51.83
76.35

92.90
98.40
121.87
144.54

Unknown sample, cubic

Determine:
1) The crystal structure
2) Lattice parameter

5 steps for the determination of crystal structure

1) Start with 2 values and generate a set of sin2 values
2) Normalise the sin2 values by dividing it with first entry

3) Clear fractions from normalised column: Multiply by

common number
4) Speculate on the hkl values that, if expressed as
h2+k2+l2, would generate the sequence of the clear
fractions column

5) Compute for each sin2 /(h2+k2+l2) on the basis of the

assumed hkl values. If each entry in this column is identical,
then the entire process is validated.
Courtesy: Sadoway

Sin2

Sin2/Sin21

Clear
fractions

(hkl)?

sin2 /(h2+k2+l2)

44.48

0.143

1.00

111

0.0477

51.83

0.191

1.34

200

0.0478

76.35

0.382

2.67

220

0.0478

92.90

0.525

3.67

11

311

0.0477

98.40

0.573

4.01

12

222

0.0478

121.87

0.764

5.34

16

400

0.0477

144.54

0.907

6.34

19

420

0.0477

Courtesy: Sadoway

The (h2 + K2 + l2) derived from extinction rules

SC

BCC

10

12

14

FCC

11

12

nd
2

Technique

Laue diffraction
This was proposed by Von Laue, got noble prize in
1914

 variable, fixed

Spot pattern
Courtesy: Sadoway

Rotational symmetry
(1) (001) Plane of cubic: 4 fold rotational
symmetry
(2) (011) plane of cubic: 2 fold rotational
symmetry
(3) (111) plane of cubic: 3 fold rotational
symmetry

By looking at the symmetry of Laue pattern one can

tell which atomic plane of crystal are we looking at

Laue spot pattern

Courtesy: Sadoway