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