X-ray Diffraction

Max von Laue won the 1914 Nobel Prize

“for his discovery of the diffraction of
x-rays by crystals.”

His measurements showed that x-rays were

photons, and additional value of his work
came in the relation of the x-ray diffraction
patterns to crystal structure.

He later went on to direct the

Fritz Haber Institute in Berlin in 1951.

Max von Laue (1879-1960)

X-Rays are photons:
λ = 10 nm to 10 pm
ν = 3e16 to 3e19 Hz.

E = 124 ev to 124 keV

X-Rays are created

by ejection of a 1s
electron followed
by filling from a
higher shell.
X-Rays are photons:
The transitions are labelled K
if the final state is n=1 (1s),
and L if the final state is n=2
(2s or 2p).

The transitions are

sub-labelled α β γ...
based on the initial
state of the electron
that is filling the hole.
 X-ray Diffraction

A monochromatic x-ray beam passing

through an Al foil creates a pattern of
rings on a photographic plate.

These diffraction rings are observed

at specific angles relative to the
crystal surface.
 The W. H. Bragg/W L. Bragg father and son team won the 1915
Nobel Prize (the very next year) for providing a quantitative
understanding of these diffraction patterns.

nλ = 2dsinθ
where
n = integer order of diffraction.
λ= wavelength,
d = crystal spacing,
θ = angle of x-rays relative to surface.

William H. Bragg William L. Bragg

(1862 – 1942) (1890 – 1971)
To understand the Bragg equation, let's first remember
the concepts of constructive and destructive interference:

constructive

destructive
 Bragg Diffraction

Constructive interference between x-rays reflected from two

adjacent atomic layers leads to angle dependent diffraction.
Let’s derive the Bragg Eq.:
1. Compared to ray 1, ray 2









travels an extra distance









BC + CB’ = 2BC.

ray 1

ray 2
Let’s derive the Bragg Eq.:
1. Compared to ray 1, ray 2









travels an extra distance









BC + CB’ = 2BC.








2. This extra distance must equal a multiple of









λ in order for the interference with ray 1









to be constructive: nλ = 2BC.

ray 1

ray 2
Let’s derive the Bragg Eq.:
1. Compared to ray 1, ray 2









travels an extra distance









BC + CB’ = 2BC.








2. This extra distance must equal a multiple of









λ in order for the interference with ray 1









to be constructive: nλ = 2BC.








3. Since AC is the hypothenuse of a right triangle









ABC, BC = dsinθ.









ray 1

ray 2
Let’s derive the Bragg Eq.:
1. Compared to ray 1, ray 2









travels an extra distance









BC + CB’ = 2BC.








2. This extra distance must equal a multiple of









λ in order for the interference with ray 1









to be constructive: nλ = 2BC








3. Since AC is the hypothenuse of a right triangle









ABC, BC = dsinθ.








4. So, nλ= 2BC = 2dsinθ Q.E.D.
ray 1

ray 2
Thus, when 2dsinθ = nλ, there is constructive interference.

ray 1

ray 2
Let’s do an example:
A polycrystalline sample scatters a beam of x-rays of wavelength 0.7093Å
at an angle of 2ϴ of 14.66o. If this is a second-order Bragg reflection
(n=2), compute the distance between the parallel planes of atoms from
which the scattered beam appears to have been reflected.
Let’s do an example:
A polycrystalline sample scatters a beam of x-rays of wavelength 0.7093Å
at an angle of 2ϴ of 14.66o. If this is a second-order Bragg reflection
(n=2), compute the distance between the parallel planes of atoms from
which the scattered beam appears to have been reflected.

solution: 1) Solve the Bragg’s Law for d:

nλ
d=
2 sin θ

€
Let’s do an example:
A polycrystalline sample scatters a beam of x-rays of wavelength 0.7093Å
at an angle of 2ϴ of 14.66o. If this is a second-order Bragg reflection
(n=2), compute the distance between the parallel planes of atoms from
which the scattered beam appears to have been reflected.

solution: 1) Solve the Bragg’s Law for d:

nλ
d=
2 sin θ

2) Substitute:

€ nλ 2(0.7093Å)
d= = = 5.559Å
2 sin θ 2 sin(14.66 / 2)
Voilà!
 X-Ray Diffraction yields lattice
parameters & atomic positions

Bragg Equation:
nλ = 2dsinθ
 Why Rings?

Thin foil Single Crystal

Polycrystalline Samples give ring patterns. Single

crystal samples yield two dimensional arrays of spots.
Polycrystalline samples average over all orientations.
a “grain”
a “grain
boundary”
 Powder XRD Measurements

The XRD powder pattern

can be used to determine
the lattice parameters of
the crystal.

As the sample is
rotated through an
angle θ, the detector
needs to be rotated
through an angle 2θ

Source: X-Ray tube Detector: Si-Li

A typical XRD powder pattern. The data is usually
plotted as a function of 2θ (detector travel).

Polycrystalline Iron
A typical XRD powder pattern. The data is usually
plotted as a function of 2θ (detector travel).

A mixture of the two phases of TiO2

Anatase and Rutile
Let's take a look at the possible diffraction patterns for this 2-D crystal.

d = a for this diffraction ring.

Let's take a look at the possible diffraction patterns for this 2-D crystal.

d ≠ a, diffraction occurs at a different angle

Let's take a look at the possible diffraction patterns for this 2-D crystal.

d ≠ a, diffraction occurs at yet another different angle

The various diffraction peaks are identified with Miller indices.
(We won't go into how to get these, but it's not hard.).

Diffraction peaks at (110), (200) and (211)

 Single Crystal X-Ray Measurements

Thin foil Single Crystal

Polycrystalline samples give ring patterns. Single

crystal samples yield two dimensional arrays of spots,
and can be used to determine the atomic positions in
the unit cell.
 Single Crystal X-Ray Measurements

Simple lattice types are

easy to characterize,
but more complex
crystals require more
sophisticated data analysis.

XRD pattern for diffraction from the

(1,0,0) face of an fcc crystal
The good news is that nowadays,
ANY molecule that crystallizes into a regular
lattice can be analyzed. Even proteins!
X-ray diffraction-quality
crystals. (a) A typical
crystal of Y. pestis SspA
with dimensions of 0.1 ×
0.1 × 0.1 mm. (b) X-ray
diffraction at 2.0 Å of
the crystal at the
National Synchrotron
Light Source.
Lots of diffraction spots are obtained from many
different incident angles on the crystal.
In the case of complex molecules,
we use the x-ray diffraction data to
produce a model, back calculate
the pattern again, and adjust
the model until it fits the pattern.
RNA polymerase - MW≈400 kDa or 400,000 g/mol

Structure obtained from the X-ray diffraction data!

RNA Ribosome 50S subunit

Structure obtained from the X-ray diffraction data!

50S Subunit of the Ribsome

The model of 50S determined in 2000 by the Steitz lab includes

2711 of the 2923 nucleotides of 23S rRNA, all 122 nucleotides of
its 5S rRNA, and structure of 27 of its 31 proteins.

Structure obtained from the X-ray diffraction data!

 X-Ray Diffraction yields lattice
parameters & atomic positions

Bragg Equation:
nλ = 2dsinθ
Let's use this data to understand crystal packing!
Back to the Future: Crystal Packing (again!)

For crystals of elemental solids,

there are some fundamental
packing structures:

fcc (Face Centered Cubic)

bcc (Body Centered Cubic)
hcp (Hexagonally Close Packed)
Diamond Structure

We have looked at the fcc and

bcc crystal lattices previously.
 Face-Centered Cubic (fcc) Crystal Lattice

r = (√2/4)a

4 atoms/unit cell
fcc Argon 74% packing efficiency
a = 526.0 pm
r = 186.0 pm

Also called cubic close packed (ccp)

 Body-Centered Cubic (bcc) Crystal Lattice

r = (√3/4)a

2 atoms/unit cell
bcc Lithium 68% packing efficiency
a = 349.0 pm
r = 151.1 pm
 Hexagonal Close Packed (hcp) Crystal Lattice

Rhombohedral unit cell

(60° angle)

AB = r
BC = (√3/3)r
a r = a/2
60°
AC = (2√3/3)r
a
 Hexagonal Close Packed (hcp) Crystal Lattice

Rhombohedral unit cell

(60° angle) r = a/2
2 atoms/unit cell
74% packing efficiency

Examples: Co, Ti, Ru

Co: r =125 pm
Ru: r =134 pm

60°
a Ti: r =147 pm
a
 Hexagonal Close Packed (hcp) Crystal Lattice

Hexagonal unit cell Rhombohedral unit cell

 Hexagonal Close Packed (hcp) Crystal Lattice
hcp versus fcc packing:

fcc

hcp
In addition to fcc, bcc and hcp, there is the Diamond Lattice:

The diamond lattice is a is a face-centered lattice,

with 4 additional atoms also occupying half of the
tetrahedral interstices.
Examples: Carbon, Silicon and Germanium.
In addition to fcc, bcc and hcp, there is the Diamond Lattice:

r = (√3/8)a
8 atoms/unit cell
34% packing efficiency

The diamond lattice is a is a face-centered lattice,

with 4 additional atoms also occupying half of the
tetrahedral interstices.
Examples: Carbon, Silicon and Germanium.
Question: The density of silicon is 2.33 g/cm3. Calculate the
lattice constant and Si-Si distance in a Si crystal.

mass mass
density = = 3
volume a

mass
a=3
€ density

( 8atoms ) 28.09g / mol −22

mass = 23
= 3.7317x10 g
dia.unitcell
€ 6.022x10 atoms / mol
Question: The density of silicon is 2.33 g/cm3. Calculate the
lattice constant and Si-Si distance in the crystal.

−22
mass 3.7317x10 g −8
a=3 = 3
3
= 5.4306x10 cm = 5.43Å
density 2.33g / cm

a = 543 pm

Si-Si distance =2r = 2(√3/8)a = 235 pm

Compound Lattices:
An example: zinc blende (ZnS) structure

3D view!
ionic bonding or covalent bonding?
An example: zinc blende (ZnS) structure

Atoms of one type occupy FCC lattice positions

Top view:
An example: zinc blende (ZnS) structure
Atoms of second type fill half of the
tetrahedral holes (diamond lattice).

Top view:
Let’s calculate the packing efficiency for a fcc crystal:
the packing efficiency, f, is the ratio between the
volume of the atoms in the unit cell,Vatoms, and the
total unit cell volume,Vcell:

Vatoms
f =
Vcell

since it contains four atoms, the fcc unit cell is characterized by:

€ ⎛ 4 3 ⎞ 16πr 3
Vatoms = 4⎜ πr ⎟ =
⎝ 3 ⎠ 3
Let’s calculate the packing efficiency for a fcc crystal:
using 4r = 2a , the total volume of the fcc unit cell is just:

3 3
3
⎛ 4r ⎞ 64r
€ Vcell = a = ⎜ ⎟ =
⎝ 2 ⎠ 2 2

taking the ratio between Vatoms and Vcell, we get:

€ 3
16πr 16π
Vatoms 3 3 32π 2
f = = 3
= = = 0.74
Vcell 64r 64 3( 64)
2 2 2 2