Structure Factor

Numerical evaluation of F(hkl)

Structure Factor

Where fj is amplitude wave scattered at atom j which depend on atomic number. Jj is phase of wave, depend on position of atom j F(hkl) is structure factor.

Structure Factor
 

F(hkl) can be presented in the form F(hkl) = A + iB

Intensity of reflection directly proportional to squared amplitude where

Now we can understand the relationship between intensities of reflection and the structure. They depend on nature and position of atoms in the unit cell

Numerical evaluation of F(hkl)

 

Although calculated structure factor determinations are carried out by computer, it is valuable to evaluate a few examples by hand, to gain an appreciation of the steps involved. As an example, the calculation of the structure factor and intensityfor the 200 reflection from a crystal of the rutile form of TiO2 (tetragonal system) a =b = 0.4594 nm, c = 0.2959 nm. Atom positions: Ti: 000;

Numerical evaluation of F(hkl)

The calculation proceeds in the following way

 

Determine the atomic scattering factors for Ti and O (see on next graph) fTi = 15.513, fO = 5.326. Calculate the phase angles J = (2T hxi + kyi + lzi) of the waves scattered by each of the atoms in the unit cell.

Numerical evaluation of F(hkl)

F cos(J) = f1 cos(J1) + f2 cos(J2) +.... + fn cos(Jn) = the sum of last column F sin(J) = f1 sin(J1) + f2 sin(J2) +... + fn sin(Jn) = 0 tan(J) = (f1 sin(J1) +... + fn sin(Jn))/f1 cos(J1)+.... + fn cos(Jn) = 0 F(200) is given by adding the values in the final column F200 = 13.79 Calculated intensity I200 = |F200|2 = 186.18 This procedure is repeated for all of the other hkl reflections from the unit cell

Structure Factor
Systematic Absences

Symmetry and Intensities

Symmetry elements define the space group of a crystal. They also define some (hkl) planes have F(hkl) = zero, and so will never give rise to a diffracted beam, irrespective of the atoms present. Such missing diffracted beams are called systematic absences In practice, we use systematic absences to detect the symmetry and so, the space group.

Systematic absences
   
N

Assume a C based centered Bravais lattice What type of symmetry involved? (x,y,z) and (x+1/2, y+1/2, z) are equal F(hkl) =
1 1 2Ti ( h x i   k y i   lz i ) 2 2 ! g i .e 2Ti ( hx i  ky i  lz i )  g i .e i N /2

g i .e 2Ti ( hx i  ky i  lz i )
i

1  e

h k 2Ti (  ) 2 2

N / 2  i .e 2Ti ( hxi  kyi  lzi ) g i

Systematic absences
Where
h k 2Ti ( ) 2 2 =1+ cosT(h+k)+ isin T(h+k)

 1 e 1+ cosT(h+k) = 2 if (h+k) is even  =

= 0 if (h+k) is odd. (h+k) = 2n called reflection conditions or conditions for observation (h+k) 2n called systematic absences

Structure Factor
Refinements

Structure determination An overview

The procedure of structure determination from a single crystal X-ray diffraction experiment can be summarised in the steps below. Obtain an accurate set of intensity values. Obviously, this is essential as everything else depends upon this raw data. The correction factors, as well instrumental factors associated with the geometry of the diffractometer, must be taken into account. Determine the unit cell and index the diffracted reflections in terms of hkl. Determine the point group and space group of the crystal, making use of systematic absences. Construct a possible model of the crystal, using physical or chemical intuition, or established techniques for solving the phase problem

Structure determination An overview

Compare the intensities, or, more usually, the structure factors, expected of the model tructure with those obtained experimentally. Adjust the atom positions in the model repeatedly to obtain improved agreement between the observed and calculated values. This process is called refinement. The crystal structure is generally regarded as satisfactory when a low value of the reliability factor, residual, or crystallographic R factor, is obtained.

Structure determinations for well crystallised inorganic or metallic compounds have R values of the order of 0.03. The values of R for organic compounds or complex molecules such as proteins are generally higher.

Powder X-ray diffraction

introductions


 

Although powder diffraction may not be the firs tchoice for structure determination, powder X-ray diffraction is used routinely for the identification of solids, especially in mixtures, in a wide range of sciences from geology to forensics. The powder is prepared into a flat plate, by applying it to sticky tape or a similar adhesiveand is irradiated with a beam of X-rays. The sample contains infinitive number of crystals in a random orientations. Each hkl plane locate on all directions, so having some positions (or directions) can reflect the incident beam.

In such random orientation case the diffraction pattern from a powder placed in the path of an X-ray beam gives rise to a series of cones rather than spots Since inter angle between incident bean and diffracted beam is then 2 so the angle at the apex of a cone of diffracted rays is 4 where is the Bragg angle.

Intensity of line in XRD

The intensities of the diffraction lines depend upon the factors already mentioned ??? An important factor is the multiplicity of the reflections in the powder pattern, p, the number of hkl having the same intensity and angle. (some reflection having different intensity but the same angle also make a increasing in intensity) In general, p will depend upon the unit cell type. For any (hkl) reflection the multiplicity will be at least two (hkl) and (-h,-k,-l)

SnO2 (a = 0.473; c = 0,318) PbO2 (a = 0.484 nm; c = 0,327)

Intensity (a.u)

x = 0.5 x = 0.4 x = 0.3 x = 0 .2 x = 0.1

20

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100

2 - Theta Scale
Gi n nhi u x c a h perovskite La1-xPbxMnO3

Scherrer Equation


A empirical equation relates roughly the averaged size of particle to broadening of peaks in diffraction pattern.

where is the mean size of the ordered particle, K is the shape factor having value of 0.9 1.1 depend on its shape, is the x ray wavelength, is the line broadening at half the maximum intensity (FWHM) in radians, and is the Bragg angle. Note! Is equation only can apply for nano particles having size 20 200 nm.