Ovidiu Garlea
Neutron Scattering Sciences Division
Oak Ridge National Laboratory
based on materials presented by
Juan Rodríguez-Carvajal
Institute Laue-Langevin, Grenoble
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Juan Rodríguez-Carvajal (ILL, LLB, France)
CrysFML, FullProf, BasIreps, Simbo, Enermag, Polar3D,…
Javier González-Platas (ULL, Tenerife, Spain)
CrysFML, GUIs, GFourier, EdPCR
Contributors:
Thierry Roisnel (LCSIM, Rennes, France): WinPLOTR
Oscar Baltuano (IPEN, Peru): WinPLOTR-2006
Carlos Frontera (ICMAB, Barcelona, Spain): Polarized neutrons
Marc Janoschek (PSI, Villigen, Switzerland) 3D-Polarimetry
Laurent Chapon & Aziz Daoud-Aladine (ISIS, U.K.) T.O.F., FP_Studio
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http://www.ill.eu/sites/fullprof/
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A set of crystallographic programs (FullProf, WinPLOTR, EdPCR…) developed for Rietveld analysis of neutron or X-ray powder diffraction, but with capabilities for single crystal and having many useful utilities
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FP_Suite_Toolbar: Program for accessing the whole set of the FullProf Suite.
WinPLOTR / WinPLOTR-2006: Programs for visualizing powder diffraction
patterns. Fitting independent peaks (CW and TOF), interface for FullProf
FullProf : Crystal and magnetic structure refinement, powder/single crystals,
polarized neutrons, multiple patterns, simulated annealing
EdPCR: Editor of the FullProf input control file
GFourier and Bond_Str.: Fourier and distance/angle calculations.
SuperCell/K_Search: Searching propagation vectors
BasIREPS: Program for calculating basis functions of irreducible representations of
space groups.
Fp_Studio: Program for visualizing crystal and magnetic structures
Check_Group: Program for finding the space group (powders and single crystals)
Datared/GDatared: Program for single crystal data reduction
Mol_tpcr: console utility for creating Rigid body groups
External programs: DICVOL04, TREOR90, ITO, XLENS
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Reading the X-ray and neutron diffraction patterns
Automatic peak search for indexing
Saving peaks as DICVOL04, Treor90, K-Search ...
Running indexing programs
Automatic generation of PCR file for cell refinement and
integrated intensity extraction
Making individual peak fit
Exporting a background file
Invoking other programs (can access the whole FullProf Suite)
Program to visualize the
diffraction patterns
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Access to other programs:(e.g., periodic table of elements, space
groups info, molecular weight and unit
cell volume calculation …)
Individual peak fit
Automatic peak & background search
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Search for the magnetic
propagation vector (k-search)
2D contour plot 3D surface plot
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A program for :
Simulation of powder diffraction patterns
Pattern decomposition integrated intensities
Crystal and magnetic structure refinement
Powder and single crystal data
Structure determination capability: Simulated
annealing on integrated intensity data
Flipping ratio refinements
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Program features include:
Multiple data sets: simultaneous treatment of several
powder diffraction patterns (CW X-rays & neutrons,
Energy dispersive X-rays, TOF neutron diffraction)
Combined treatment of single crystal and powder data
Automatic mode for handling refinement codes and
symmetry constraints
Rigid body refinements + distances and angles restraints
Special form factors
The treatment of micro-structural effects
Sequential refinement
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Documented in “fp2k.inf” or…to the Fullprof homepage at “What’s new”
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Minimal input:
Input control file (extension “.pcr ”): PCR-file
Model, crystallographic / magnetic information,
Experimental parameters
Eventually, experimental data
(Format depending on the instrument)
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Many variables and options
Complex to handle
USE the GUI:
EdPCR
Hint: copy an existing PCR-file
and modify it for the user case,
or...
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Imports crystal structures
from CIF and SHELX files
Constraints: reduce the number of
free parameters (rigid body refinements)
Restraints: same number of free
parameters + additional observations
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Let's get specific !
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Modeling the entire
diffraction pattern( )ci i iy I T T b h h
h
*
hhhhh MM *NNIFor unpolarized neutrons:
hM e M(h) e M(h) e (e M(h))
Complete structural
model should be
provided
LaMnO3 :
50K and 150 K
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magnetic moment
expanded as Fourier series
k
k kRSm ljsljs iexp 2
l : index of a direct lattice point
j : index for a Wyckoff site (orbit)
s: index of a sublattice of the j site
Skjs : Fourier coefficients
are complex vectors
1( )exp{ 2 }
2k k k kS R Ii i
… at the origin : m = ∑Sk
Necessary condition for
real moments
jsjs kk- SS
The magnetic structure factor:
1
2kM h h S H k t rn
j j j js jsj s
p O f T exp i S
ts
S Symmetry operators
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two different ways of treating magnetic structures:
The magnetic symmetry is introduced together with explicit
symmetry operators of the crystal structure.
The refined variables are directly the components of the Skjs vectors.
1 2k k kS Sjs js j jM exp i A relation exist between Skj1 and Skjs
Fourier coefficients as linear combinations of the basis functions of the
irreducible representation of the propagation vector group Gk
The basis functions of the IRs are introduced together with explicit
symmetry operators of the crystal structure.
The refined variables are directly the coefficients C1, C2, C3, ….
k
kS Sjs n n
n
C js
.
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Magnetic phase
!
!Nat Dis Mom Pr1 Pr2 Pr3 Jbt Irf Isy Str Furth ATZ Nvk Npr More
1 0 0 0.0 0.0 1.0 1 0 -1 0 0 0.000 0 7 0
!
P m m m <--Space group symbol
!Nsym Cen Laue MagMat
4 1 3 1
!
SYMM x,y,z
MSYM u,v,w,0.0
SYMM -x,-y,z+1/2
MSYM -u,-v,w,0.0
SYMM -x+1/2,y+1/2,-z+1/2
MSYM u,-v,w,0.0
SYMM x+1/2,-y+1/2,-z
MSYM -u, v,w,0.0
!
!Atom Typ Mag Vek X Y Z Biso Occ Rx Ry Rz
! Ix Iy Iz beta11 beta22 beta33 MagPh
Mn1 MMN3 1 0 0.50000 0.00000 0.00000 0.04338 1.00000 0.000 3.847 0.000
0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
0.000 0.000 0.000 0.000 0.000 0.000 0.00000
0.00 0.00 0.00 0.00 0.00 0.00 0.00
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!Nat Dis Mom Pr1 Pr2 Pr3 Jbt Irf Isy Str Furth ATZ Nvk Npr More
1 0 0 0.0 0.0 1.0 1 0 -2 0 0 0.000 0 7 0
!
P m m m <--Space group symbol
! Nsym Cen Laue Ireps N_Bas
4 1 1 -1 3
! Real(0)-Imaginary(1) indicator for Ci
0 0 0
!
SYMM x,y,z
BASR 1 0 0 0 1 0 0 0 1
BASI 0 0 0 0 0 0 0 0 0
SYMM -x+1,-y,z+1/2
BASR -1 0 0 0 -1 0 0 0 1
BASI 0 0 0 0 0 0 0 0 0
SYMM -x+1/2,y+1/2,-z+1/2
BASR 1 0 0 0 -1 0 0 0 1
BASI 0 0 0 0 0 0 0 0 0
SYMM x-1/2,-y+1/2,-z
BASR -1 0 0 0 1 0 0 0 1
BASI 0 0 0 0 0 0 0 0 0
!
!Atom Typ Mag Vek X Y Z Biso Occ C1 C2 C3
! C4 C5 C6 C7 C8 C9 MagPh
Mn1 MMN3 1 0 0.50000 0.00000 0.00000 0.04338 1.00000 0.000 3.847 0.000
0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
0.000 0.000 0.000 0.000 0.000 0.000 0.00000
0.00 0.00 0.00 0.00 0.00 0.00 0.00
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more specific …
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I. Well defined crystallographic structure model (FullProf)
Peak positions of
magnetic reflections
Cell parameters
II. Determine the propagation
vector(s) (k-Search)
Propagation vector
Space Group
Atom positions
III. Perform Symmetry Analysis
(BasIreps)
Atomic components
of basis functions
IV. Introduce and refine by LSQ
the magnetic phase (FullProf)
Structure solution
Simulated annealing (FullProf)
for more complicated structures
Extracted integrated
intensities
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Extract (Profile matching),
, ,
,
( )( )' '
( )
i k obs i i
obs k calc k
i calc i i
T T y BI I
y B
Constraint the obtained models (representation analysis)
Refine them back the with the Rietveld method
2 2 2
, ,( ( ))n obs n calc k I
n k
M w G G
Minimize the difference between the observed and the calculated
integrated intensities against the parameter vector I
use spherical components of Fourier coefficients
better control of the amplitude
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Code of files
Working
directory
Title
Space group
symbol
or generators
Brillouin
Zone label k-vector
Axial/polar
Number of
atomsAtoms
positions
Atoms in
Unit Cell
BasIreps provides the basis functions (normal modes) of the
irreducible representations of the wave-vector group Gk
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k=(0,0,0), =1, n=1,2,3
=1, j=1, s=1,2,3,4
Format for FullProf
jsn
kS
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visualising crystal and magnetic structures
input file has the extension ".fst" and it is automatically
generated by FullProf after a structure refinement
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Examples and tutorials can be
found in the Web page of the
FullProf Suite at ILL
http://www.ill.eu/dif/fullprof