Structure elucidation from

XRD

X-rays are electromagnetic waves with a wavelength in the range of interatomic

distances (0.1-10 Å)
 topics
• Highlight on instrumentation
• Crystallography
• X-ray diffraction from polycrystalline
samples (powders);
• XRD data interpretation
Instrumentation highlight

Details should be given in

Instrumentation lecture !
Shimadzu XRD-6000

xrd-6000-pharma.ppt
What is X-ray Diffraction?
monochromatic/single wavelength
with highest intensity is used as
the X-ray source
 Powder diffractometers typically use the Bragg-
Brentano geometry.

Detector
X-ray
tube

w q 2q

• The incident angle, w, is defined between the X-ray source and the sample.
• The diffracted angle, 2q, is defined between the incident beam and the
detector angle.
• The incident angle w is always ½ of the detector angle 2q .
• In a q:2q instrument (e.g. Rigaku RU300), the tube is fixed, the sample
rotates at q °/min and the detector rotates at 2q °/min.
• In a q:q instrument (e.g. PANalytical X’Pert Pro, Bruker), the sample is fixed
and the tube rotates at a rate -q °/min and the detector rotates at a rate of q
°/min.
 θ - 2θ Scan

The θ - 2θ scan maintains these angles with the

sample, detector and X-ray source
Normal to surface

Only planes of atoms that share this normal will be seen in the θ - 2θ Scan
 Bragg’s law is a simplistic model to understand
what conditions are required for diffraction.

l  2d hkl sin q q q

dhkl dhkl
• For parallel planes of atoms, with a space dhkl between the planes, constructive
interference only occurs when Bragg’s law is satisfied.
– the X-ray wavelength l is fixed.
– Consequently, a family of planes produces a diffraction peak only at a specific angle q.
– Additionally, the plane normal must be parallel to the diffraction vector
• Plane normal: the direction perpendicular to a plane of atoms
• Diffraction vector: the vector that bisects the angle between the incident and
diffracted beam
• The space between diffracting planes of atoms determines peak positions.
• The peak intensity is determined by what atoms are in the diffracting plane.
constructive interference results in diffraction line, but destructive interference does not
Peaks result from This is an example of an
constructive XRD spectrum for quartz.
interference for the
reflected X-rays
 Solid matter

crystalline non-crystalline B
A [101]
The atoms are (amorphous)
arranged in a The atoms and A
regular pattern, molecules are arranged A
A
and there is as in a random way similar A

Intensity (a.u)
smallest volume to the disorder we find in
element that by a liquid  do not form
repetition in three crystallites. Glasses are
dimensions amorphous materials. 5h
Am
describes the Small particles with no 4h
crystal (a unit long-range order (100
3h
cell). Ǻ) 2h
Long range order single crystal
(>103 molecules) 10 20 30 40 50 60 70 80 90
Solid which contains
polycrystalline 2q (o)
single crystallite
Solids which contain
many small, randomly
oriented and joined
crystallites/grains
Quartz (SiO2), a crystalline solid and the
most abundant mineral in the earth’s crust)

Fig. 10.2: Crystalline solids are

characterized by highly ordered arrays of
atoms, ions or molecules and give distinct
X-ray diffraction patterns.
Amorphous solids have no long-range
ordering in their structures.
What type of attractive forces are most
important in the quartz structure?

Glass (SiO2), has the same chemical

composition as quartz but exhibits no
extensive, repeating organization.
Crystalline Versus Amorphous
Quartz Obsidian
Polymers are made up of repeating units “mers”, that make up a long chain.
The chain may be cross-linked, or held together with van der Waals or
hydrogen bonds

Kristal XRD MSE630 Lecture1.ppt

Structures may be crystalline, having repeating structure, or
amorphous, having local structure but no long-range structure

Kristal XRD MSE630 Lecture1.ppt

 Crystalline materials are characterized by the
orderly periodic arrangements of atoms.
The (200) planes The (220) planes
of atoms in NaCl of atoms in NaCl

• The unit cell is the basic repeating unit that defines a crystal.
• Parallel planes of atoms intersecting the unit cell are used to define
directions and distances in the crystal.
– These crystallographic planes are identified by Miller indices.
 The atoms in a crystal are a periodic array of
coherent scatterers and thus can diffract light.
• Diffraction occurs when each object in a periodic array scatters
radiation coherently, producing concerted constructive interference
at specific angles.
• The electrons in an atom coherently scatter light.
– The electrons interact with the oscillating electric field of the light wave.
• Atoms in a crystal form a periodic array of coherent scatterers.
– The wavelength of X rays are similar to the distance between atoms.
– Diffraction from different planes of atoms produces a diffraction pattern,
which contains information about the atomic arrangement within the
crystal
• X Rays are also reflected, scattered incoherently, absorbed,
refracted, and transmitted when they interact with matter.
• Only crystallites having reflecting planes (h,k, l)
parallel to the specimen surface will contribute to
the reflected intensities.
• If we have a truly random sample, each possible
reflection from a given set of h, k, l planes  an
equal number of crystallites contributing to it.
• We only have to rock the sample through the
glancing angle THETA in order to produce all
possible reflections.
 X-ray Powder Diffraction Particle size
and defects

Peak shapes

Peak relative
intensities

Background Atomic
Peak distribution in
positions the unit cell
10 20 30 40
2q

Unit cell Diffuse scattering,

c Symmetry sample holder,
and size matrix, amorphous
b phases, etc...
a
ANATOMI DIFRAKTOGRAM XRD
 Background

Sinyal yang diinginkan

Noise
 X-Ray Powder Diffraction (XRPD) uses information about
the position, intensity, width, and shape of diffraction peaks
in a pattern from a polycrystalline sample.

The x-axis, 2theta, corresponds to the angular position of the detector

that rotates around the sample.