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X RAY DIFFRACTION AND BRAGGS LAW

X RAY DIFFRACTION
For visible electromagnetic radiation to be diffracted, the spacing between lines in a 2d grating must be of the same order as wave length range of light. X ray is suitable. (Atomic spacing) Electrons at high speeds directed to a metal target: part of their KE is converted into X rays. X rays emitted by target has continuous range of wavelengths called as white radiation. Characteristic x-rays: Emitted from heavy elements when electrons transition between the lower atomic energy levels. (at high Voltage)

K- alpha radiation high intensity hence used in diffraction studies. X rays directed at the crystal interacts with the electrons of the atoms.

Electrons oscillate and form a source of electromagnetic radiation. Emitted waves have same frequency as that of X rays- in all directions Emission in a particular direction is a combined effect of oscillations of electrons of all the atoms. Emissions in phase reinforce one another in only specific directions, depending on the direction of incident X rays, their wavelength and the spacing between the atoms in crystal. Destructive interference results in other directions. The waves emitted will have same frequency as incident rays.

Diffraction of X rays by planes of atoms: Constructive and non constructive interference

BRAGGS LAW
Easiest way to visualize the diffraction effects produced by 3-d grating (A diffraction grating is an optical component with a regular pattern, which splits and diffracts light into several beams travelling in different directions) Braggs Law: Make the phases of the beams coincide when the incident angle equals and reflecting angle. A beam of x rays of wavelength is directed towards the crystal at an angle to the atomic planes. The 2nd beam continues to the next layer that is scattered by atom B. The 2nd beam must travel the extra distance AB + BC if the two beams are to continue traveling adjacent and parallel.

This extra distance must be an integral (n) multiple of the wavelength () for the phases of the two beams to be the same. n = AB+BC, where is the wavelength of the incident X-ray beam, dhkl is the distance between atomic layers in a crystal, is angle of incidence. n = AB + BC but AB = dhkl sin and AB = BC, results as n= 2dhkl sin (the location of the surface does not change derivation)

The reflection of x rays is by the atomic planes. for n=2 and for the plane (100) and for n=1 and the plane (200) ?? Interplanar spacing of (100) plane is twice that of for (200) plane; similarly for n=3 and for the plane (300) and so on.. Take n=1 and for all reflections for all parallel planes as (100), (200) if there is no (200) plane with atoms on it, then what is designated as (200) reflection actually refers to the second order reflection from (100) plane. For cubic crystals, the relation between inter planar

Q. A diffraction pattern of a cubic crystal of lattice parameter a= 3.16 Ao is obtained with a monochromatic x-ray beam of wavelength 1.54Ao. The first four lines of this pattern were observed to have the following values. Determine the inter planar spacing and the miller indices of the reflecting planes. (n=1) Solution: Step 1: Evaluate d (inter planar spacing) for all lines Step 2: Find (h2+k2+l2) =(a/d)2 values. Step 3: Arrive the possible hkl values.

Line 1 2

d A0 20.3 29.2

(h2+k2+l2) =(a/d)2 2 4

hkl 110 200

3
4

36.7
43.6

6
8

211
220

THE POWDER METHOD


Experimental technique to determine crystal structures. The K-alpha radiation is allowed to incident on thousands of randomly oriented crystals in powder form. A Debye- Scherrer camera; consists of a cylindrical cassette with a strip of photographic film positioned round the circular periphery. If the sample consists of some tens of randomly orientated single crystals, the diffracted beams are seen to lie on the surface of several cones. The cones may emerge in all directions, forwards and backwards. A sample of some hundreds of crystals (i.e. a

A circle of film is used to record the diffraction pattern as shown. Each cone intersects the film giving diffraction lines. The reflected radiation thus lies on the surface of the cone whose apex is at the point of contact of the incident radiation with the specimen. And since the inter planar spacing d being the same for all the members of the family of crystal planes, they all reflect at the same Bragg angle hence lying on the same cone. For n=1, many combinations of d and to satisfy Braggs Law. Each value of n represents a cone, hence powder represents many cones.

For every set of crystal planes, by chance, one or more crystals will be in the correct orientation to give the correct Bragg angle to satisfy Bragg's equation. Every crystal plane is thus capable of diffraction. Each diffraction line is made up of a large number of small spots, each from a separate crystal. Each spot is so small as to give the appearance of a continuous line. If the crystal is not ground finely enough, the diffraction lines appear speckled.

The distance between the two arc spread out film is termed S and obtained in as S=4R where is the Bragg angle expressed in radians. Ease of conversion, S is measured in mm, in degrees and camera radius to be 57.3 mm (since 1 rad=57.3o) http://www.matter.org.uk/diffraction/xray/powder_method.htm

http://www.matter.org.uk/diffraction/xray/experimental_powder_diffraction.htm

STRUCTURE DETERMINATION:
1. 2. 3. Complex structure determination is time consuming Steps to be followed are : Determining the macroscopic symmetry of the crystal The space lattice and its dimensions and finally the atomic arrangement with in the unit cell. Measurement of density of crystal and chemical composition also assists the process. If the crystal is mono atomic, the space lattice together with the lattice parameters is a complete description of the crystal structure.

From the above rules the ratio of (h2+K2+l2) values for allowed reflections from different crystals : SC 1:2:3:4:5:6:8. BCC 1:2:3:4:5:6:7:8 FCC 3:4:8:11:12:16:19:20:24:27 DC 3:8:11:16

A simple comparison of the observed ratios of sin2 values with the above is then sufficient to identify the crystal

3.18 Using a diffractometer and a radiation of wavelength 1.54A0, only one reflection from an FCC material is observed when 2 is 1210. Which plane are we talking about? What are the indices of this reflection? What is the inter planar spacing ? Show that next higher indices reflection cannot occur. Solution: Given = 1.54 A0 For FCC, 2 = 1210 From the formula, 2*d*sin()=(1)* from where d can be calculated. d= 0.8846 A0

Also d= a/(h2+k2+l2)1/2, from where a (lattice parameter) can be calculated. The next plane will be half the distance from the first plane d200= 0.8846 /2 From the above value of d, sin() can be evaluated by sin()= /2*d200 3.28 Explain why there is no end-centered cubic space lattice?

3.32 Crystal Structure? Lattice parameter (a)? If possible the element?


2 Multiplyin g factor Round off hkl

38.7 45.4 65.7 78.8 83.0 99.6 112.5 117.0 138.1 164.2

3.34 Crystal Structure? Lattice parameter (a)?? What is the minimum number of reflections you need to ascertain this structure and why? Identify the element if possible.
Multiplying factor 0.12 0.238 0.357 0.475 0.593 0.711 0.83 Round off hkl

Diffraction Techniques: Diffractometer is a apparatus uesd to determine the angles at which diffraction occurs for powdered specimens.

Schematic diagram of an x-ray diffractometer; T= x-ray source, S= specimen, C= detector and O the axis around which the specimen and the detector rotate.

4.60 The metal niobium has a BCC crystal structure. If the angle of diffraction for the (211) set of planes occurs at 75.990 (first order reflection) when a mono chromatic x-ray radiation having a wavelength of 0.1659 nm is used, compute a) The inter planar spacing for this set of planes b) The atomic radius for the niobium atom Solution: Step1: Calculate d(211) Step 2: Determine the lattice parameter, a Step 3: Calculate Radius [R=a* (3)1/2 / 4] 4.61 For which set of planes will a first order diffraction peak occur at a diffraction angle of 44.530 for FCC nickel when monochromatic radiation having a wavelength of 0.1542 nm is used? (R=(0.1246 nm) Solution: Compute the inter planar spacing Evaluate decide the plane based on [square (h,k,l)].