Rietveled refinement

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Goal of rietveled refinement
Minimize the residual function using anon linear least squares
1
algorithm = ( - )2 , =

Refine the crystal structure of compound (cell parameters ,

atomic positions and debye waller factor).
Stages in rietveld refinement:
1- decide on the initial structural model 6- refine atomic coordinates
2- refine background and overall cell 7- refine thermal parameters
3-refine unit cell dimensions 8- refine occupancies
4- refine zero point correction
5- refine peak shape

The Model (3 parts)

Crystallographic Model: describes size, symmetry of unit cell, atomic
positions, thermal parameters and occupancy
Instrumental Model: describes optics and set-up of diffractometer
Profile Model: describes peak shape Model data is minimized iteratively
until satisfactory answer, i.e. a good fitTemplates
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pattern is obtained
 Where to get crystal structure information
check if the structure is already solved websitesInorganic Crystal Structure
Database (ICSD) http://icsd.ill.fr/icsd/index.html4% is available for free online as a
demo
Crystallography Open Database http://www.crystallography.net/
Mincryst http://database.iem.ac.ru/mincryst/index.php
American Mineralogist http://www.minsocam.org/MSA/Crystal_Database.html
WebMineral http://www.webmineral.com/
databasesPDF4 from the ICDD
Linus Pauling File from ASM International
Cambridge Structure Database
literatureuse the PDF to search ICSD listings and follow the references
look for similar, hopefully iso structural, materials
index the cell, and then try direct methods or ab-initio solutions beyond the
scope

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The intensity in powder diffraction

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The scale factor =
2
: Beam intensity (depends on measurements)
: Phase volume fraction
: Phase cell volume

The Lorentz-Polarization factor (

it depends on the instrument geometry
monochromator (angle )
detector
beam size/sample volume
sample
Powerpoint positioning (angular)
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structure factor

:The multiplicity of the k reflection (with h, k, l Miller indices)

:The temperature factor N: number of atoms
xn, yn, zn :coordinates of the nth atom
Fn : atomic scattering factor

Atomic scattering factor and Debye-Waller

The atomic scattering factor for X-ray decreases with the
diffraction angle and is proportional to the number of electrons.
The temperature factor (Debye-Waller, B) accelerates the
decrease.
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profile shape function {Sj(2i-2k,j)}
different profile shape function are available:
Gaussian (the original Rietveld function for neutrons)
Cauchy
Voigt and Pseudo-Voigt (PV)
Pearson VII, etc.
For example the PV:

= + tan + tan Caglioti formula

shape parameters
=
=
gaussianity
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The texture (or preferred orientations):
The March-Dollase formula is used:

PMD is the March-Dollase parameter.

summation is done over all equivalent hkl reflections (mk).
n is the angle between the preferred orientation vector and the
crystallographic plane hkl (in the crystallographic cell coordinate
system).

The absorption factor:

1
in the Bragg-Brentano case (thick sample): Aj=2 , :is the linear absorption
coefficient of the sample
- For the thin sample or films the absorption
Powerpoint depends on 2
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- For Debye-Scherrer geometry the absorption is also not constant Page 10
background

The more used background in Rietveld refinements is a polynomial

function in 2 :
Nb :is polynomial degree
an :the polynomial coefficient

Quality of the refinement

The agreement between the observations and the model is
estimated by the following indicators:

The profile Rp Rp=
= (
)
N=number of points, P=number of parameters

The weighted profile Rwp

The expected Rexp

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Goodness of fit or the reduced 2
Rwp
2 =
Rexp
`Rwp < 0.1 correspond to an acceptable refinement with a medium
complex phase
For a complex phase (monoclinic to triclinic) a value < 0.15 is good
For a highly symmetric compound (cubic) with few peaks a value <0.08
start to be acceptable.
The goodness of fit is the ratio between the Rwp and Rexp and cannot
be lower then 1
A good refinement gives GofF values lower than 2.

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full prof programe

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