3.

012 Fund of Mat Sci: Structure – Lecture 18

X-RAYS AT WORK

An X-ray diffraction image for the Model of helical domains in myoglobin.

protein myoglobin. Source: Wikipedia. Image courtesy of Magnus Manske
3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Homework for Wed Nov 23
• Prof Wuensch Lecture Notes
• http://capsicum.me.utexas.edu/ChE386K/ for
many details (Lect 19 onwards, but note
different 2π convention)
• Buy turkey

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Last time:
1. X-rays generation: undulators and wigglers in
synchrotrons, bremsstrahlung and core
excitations (e.g. Kα) in X-ray tubes
2. Reciprocal lattice
3. Diffraction gratings – Huygens construction
4. Laue diffraction from periodic
arrays in 1-d, 2-d, 3-d (Left-pointing 1st, 2nd, and
3rd order, and all higher order
beams not shown.)
0th Order
1st Order
2nd Order
3rd Order

Groove

Incident Plane Wave (Lambda = 2/11 * Grating Pitch)

Diffraction Grating
Figure by MIT OCW.

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Reciprocal lattice (IV)
r r r r
G = hb1 + ib2 + jb3 with h, i, j integers,
r r r r r r
r a 2 ×a3 r a3 × a1 r a 1×a2
b1 = 2π r r r b2 = 2 π r r r b3 = 2π r r r
(
a1⋅ a2 ×a3 ) a1⋅ a2 ×a3 ( ) a1⋅ a2 × a3 ( )
r
G =( h, i, j ) are the reciprocal-lattice vectors
d∗hkl is distance between two planes of Miller indices h k l
2π
in the reciprocal lattice =
d hkl

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
First and second Laue conditions
r r
a ⋅ S = a cos α n
r r
a ⋅ S0 = a cos α 0
S0
r r r
a.S0
a ( cos α n − cos α 0 ) = a ⋅ S − S0 = nx λ ( )
a
a.S
S

a2
Figure by MIT OCW.
a1

Figure by MIT OCW.

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
All three Laue conditions
r r
r
(
a1 ⋅ )
S − S0 = integer multiple of λ
r r
r
(
a2 ⋅ )
S − S0 = integer multiple of λ
r r
r
(
a3 ⋅ )
S − S0 = integer multiple of λ

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Ewald construction
Diffracted beam

hkl hkl
P

d*hkl 2π
S
λ d*hkl = S-S0 2π
λ
θ
Incident beam
θ

2π/λ
θ C 2π O
S Origin of the
λ 0
Crystal at the center reciprocal lattice
of the sphere

Reflecting sphere

Figure by MIT OCW.

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
Laue condition needs “white” spectrum
202 102 002
201
Reflected
Beam 201 001
101
2π/λmax
Incident 200 100 000
Beam 200
2π/λmin
Reflected
Beam 201 101 001
201
Reflected
Beam
202 102 002
Reflecting Sphere for Reflecting Sphere for
Smallest Wavelength Largest Wavelength

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005) Figure by MIT OCW.
 Alternate geometrical view

002

001

200 100
O

001

002

Figure by MIT OCW.

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Bragg Law
P

O λ P'

O' P''

θ E θ
(hkl)
A
θ
d d
(hkl) B D
C
d
(hkl)

Figure by MIT OCW.

nλ = d hkl 2sin θ
3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Equivalence to Laue condition
Diffracted
Beam

2π S/λ ν
*
dhkl = (
S-S0 2π
λ (
2π/λ θ
Incident θ ν
Beam θ 2π S0/λ
(hkl) Reciprocal-
lattice Origin

Ewald Sphere

Figure by MIT OCW.

r r
⎛ S − S0 ⎞ 2π 2π 2π
2π ⎜ ⎟= cosν = d hkl =
∗
= 2sin θ
⎝ λ ⎠ λ d hkl λ
3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Powder diffraction (I)
202 102 002
201
Reflected
Beam 201 001
101
2π/λmax
Incident 200 100 000
Beam 200
2π/λmin
Reflected
Beam 201 101 001
201
Reflected
Beam
202 102 002
Reflecting Sphere for Reflecting Sphere for
Smallest Wavelength Largest Wavelength

Figure by MIT OCW. 3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Powder diffraction (II)

Image removed for copyright reasons. Please see the diagram at http://capsicum.me.utexas.edu/ChE386K/html/powder_diffraction_3.htm.

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Powder diffraction (III)

Diagrams of the Powder Method removed for copyright reasons.

See the images at http://www.matter.org.uk/diffraction/x-ray/powder_method.htm

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 X-ray filters

Image removed for copyright reasons.

Please see the diagrams at http://capsicum.me.utexas.edu/ChE386K/html/filter.htm.

Image removed for copyright reasons.
Please see the graph at http://capsicum.me.utexas.edu/ChE386K/html/absorption_edge.htm.

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Debye-Scherrer camera
Photographs of a Debye-Scherrer camera removed for copyright reasons.

Figure by MIT OCW.

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Interplanar spacings

2
a
Cubic: d 2
hkl = 2
h +k +l
2 2

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
Debye-Scherrer camera
λ = d hkl 2sin θ

a2
2
Cubic: d hkl = 2
h + k2 + l2

Figure by MIT OCW.

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
Tables removed for copyright reasons. See http://www.matter.org.uk/diffraction/x-ray/indexing_powder_pattern.htm

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
Systematic
absences

Image removed for copyright reasons.

Please see the table at http://capsicum.me.utexas.edu/ChE386K/html/systematic_absences.htm.

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Effects of symmetry on diffraction

Images removed for copyright reasons. Please see the images at http://capsicum.me.utexas.edu/ChE386K/html/diffraction_symmetry1.htm.

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Structure Factor

Image removed for copyright reasons.

Please see the graph at http://capsicum.me.utexas.edu/ChE386K/html/scattering_factor_curve.htm.

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Friedel’s law

• The diffraction pattern is always

centrosymmetric, even if the crystal is not
centrosymmetric

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Point symmetry + inversion = Laue

Image removed for copyright reasons. Please see the table at http://capsicum.me.utexas.edu/ChE386K/html/diffraction_symmetry2.htm.

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
Back-reflection and transmission Laue

Diagrams of the Laue Method removed for copyright reasons.

See the images at http://www.matter.org.uk/diffraction/x-ray/laue_method.htm.

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)