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Refinement
Scott A Speakman
13-4009A
x3-6887
speakman@mit.edu
space group
lattice parameters
atomic positions
atomic site occupancies
atomic thermal parameters
isotropic or anisotropic
Atom
Wyckoff x
Site
occ.
La
1a
0.00157
6f
0.1993
0.5
0.5
0.0027
Instrumental Parameters
background
peak profile parameters
cagliotti parameters u, v, w
pseudo-voigt or other profile parameters
asymmetry correction
anisotropic broadening
zero shift
specimen displacement
absorption
extinction
roughness
porosity
scale factor
2nd order polynomial background: 3 parameters
2 lattice parameters
no atomic positions (all atoms are fixed)
3 or 5 thermal parameters
2 or 4 occupancy factors
zero shift and specimen displacement
5 profile shape parameters
background functions
profile functions
vary significantly with programs
almost all programs use Cagglioti U, V, and W
H 2 W V tan U tan 2
HSP uses pseudo-voigt, Pearson VII, Voigt, or pseudo-voigt 3 (FJC
asymmetry)
GSAS uses functions derived more from neutron and synchrotron
beamlines
go to parameters_calc_pattern.pdf
Refinement Strategy
Rietveld methods fit a multivarialbe structure-backgroundprofile model to experimental data
lots of potential for false minima, diverging solutions, etc
need to refine the most important variables first, then add more
until an adequate solution is realized
a correct solution may not result
scale factor
zero shift or specimen displacement (not both)
linear background
lattice parameters
more background
peak width, w
atom positions
preferred orientation
isotropic temperature factor B
u, v, and other profile parameters
anisotropic temperature factors
Additional Files
XRD_Basics_HSP_2006.pdf
large collection of information about X-ray diffraction, instrumentation,
and different techniques
Introduction.pdf
overview of Rietveld
parameters_calc_patterns.pdf
overview of parameters involved in calculating a diffraction pattern
further reading
Rietveld refinement guidelines, J. Appl.Cryst. 32 (1999) 36-50
R.A. Young (ed), The Rietveld Method, IUCr 1993
V.K. Pecharsky and P.Y. Zavalij, Fundamentals of Powder
Diffraction and Structural Characterization of Materials,
Kluwer Academic 2003.
DL Bish and JE Post (eds), Modern Powder Diffraction, Reviews
in Mineralogy vol 20, Min. Soc. Amer. 1989.
CCP14 website http://www.ccp14.ac.uk/tutorial/tutorial.htm
prism.mit.edu/xray/resources.htm
Rietveld Programs
Free
GSAS + ExpGUI
Fullprof
Rietica
PSSP (polymers)
Maud (not very good)
PowderCell (mostly for calculating patterns and transforming crystal
structures, limited refinement)
Commercial
PANalytical HighScore Plus
Bruker TOPAS (also an academic)
MDI Jade or Ruby
Examples
Silicon
LaB6
intermetallic LaNi4.85Sn0.15
Silicon
Open the datafile in HSP
Add the structure model
insert the structure manually
import (insert) a struture file
usually use the CIF format the ubiquitous standard for crystal
structures
HSP can also import ICSD *.cry files and structures from other
refinement programs
GSAS can import CIF or PowderCell files
a=5.43 A
Si at 0.125, 0.125, 0.125
LaNi4.85Sn0.15
The data was taken from Chapter 6 of Fundamentals of Powder
Diffraction and Structural Characterization of Materials, by
Pecharsky and Zavalij
The structure is a bit more complex that our earlier example,
which allows us to explore more features of HighScore Plus
The data (Ch6_1.raw) is in GSAS format, which can be read into
HighScore Plus
I have also included a CIF file from the ICSD (#104685) with all
the main features of the structure described
Issue to Consider
How can I work without knowledge of the structure?
Use LeBail or Pawley method to determine lattice parameters
Try indexing and solving the structure using the HighScore Plus tools
You will find that there are 16 possible space groups for this material, but
picking the most common (and simplest) choice, P6/mmm, is the right way to go