Crystal Structure Approximation

Using Rietveld Refinement

Technique

ASHISH KUMAR MALL

PhD
Materials Science Programme
IIT Kanpur

Information hidden in X-ray spectrum

Extracting information from X-ray data

Search and match
ICDD or JCPDS
High Score Plus
Pearson crystal database
Indexing
Structural refinement

Rietveld refinement
Rietveld refinement is a technique devised by Hugo Rietveld
for crystalline materials.
Uses a least squares approach to refine a theoretical line profile
until it matches the observed profile.
Very useful in case of overlapped reflection, multiple phases
and complex structures.
2
1
Function,

being

the variance of the observation

Where, Wi is the statistical weight and c is an overall scale factor

such that

Useful software's
XPert High score plus
GSAS (http://www.ccp14.ac.uk/solution/gsas/ )
RIETAN
MAUD Programe
Juan Rodrguez-Carvajal
FullProf (www.ill.eu/sites/fullprof/ )
Bilbao Crystallographic Server
(http://www.cryst.ehu.es/)
Space Group Diagrams and Tables
http://img.chem.ucl.ac.uk/sgp/large/sgp.htm

In the FullProf Suite toolbar, select ED PCR tab

Following window pops up on clicking ED PCR tab.

Note all the tabs on the right hand side are inactive

Click new data to make a

new data file and all tabs
get activated.

Press the General tab and fill in the sample name at

the given space for title

Click on patterns tab to fill information related to

diffraction pattern

Click the Data file/Peak shape tab to enter the data file and peak
profile parameters

Browse for diffraction data file which should be in .dat

format

To make a data file, copy the intensity

column into notepad. At the top, enter the
value of the start angle, press space, enter
the step, space and then enter the final
angle. Save the file with .dat extension.

Click on the Refinement/simulation tab to inform

the software what you intend to do

For simulation

For refinement

Target material can be

changed as applicable

Click the pattern calculation/peak shape tab to select

the peak shape function

It is a combination of Lorentzian and

Gaussian function and holds good for
most of the profiles

Click on background tab to estimate the background

Select one of the background functions from the list

Holds good only if the background is

linear. For sloppy background,
choose linear interpolation

Click on Phases tab to enter the phase and space

group of the material

Orthorhombic
Structural model (Rietveld method)

X Ray

Pseudo-Voigt

Press symmetry tab and fill the space group and

press OK.

Pnma
Each descriptor separated by a space

Press the refinement tab and the following

window appears

Press the background tab. Insert

background parameters

Contd.

Press profile to input profile parameters

Press atoms to fill atomic information

Label: IUPAC symbol of the element with a suffix if more than one
atoms are present of the same type.
Ntyp: Simply IUPAC symbol or oxidation state if the same atom is
present with different oxidation states.
B:
Isotropic thermal parameters
Occ: No of atoms of a particular type in the unit cell

Save the file in the same folder containing the .dat file

Click on this to
Save the file

Select the parameters to vary and run the program

Click on this icon to run the program. It will promptly ask for the data file.
Browse for it and select to open it. You will see the refinement taking place.

Sequence for varying the parameters

Scale factor
Background and instrumental parameters
Lattice parameters and more background parameters
Atomic positions
Peak shape parameters
Atomic occupancies
Thermal parameters
Microstructural parameters

Crystal structure Refinement

Quality of the Refinement

n = total number of points in
the pattern minus total
number of excluded points

Weighted Profile Factor:

being

Expected Weighted Profile Factor:

Goodness of fit indicator:

the variance of the observation

P=number of parameters

Reduced chi-square:

In the VESTA Toolbar