GSAS Rietveld and EPXGUI Software Practicals

GSAS Rietveld and EPXGUI software practicals
01: P. 2
Installing GSAS, EXPGUI and example files
02: P. 3 to 14
An Easy start: refining the structure of corundum powder using

data collected on a neutron powder diffraction system
02a: P. 15 to 16
Creating a GSAS neutron instrument

parameter file using INSTEDIT
7th
Canadian Powder
Diffraction Workshop
42Hhttp://www.cins.ca/cpdw/
April 2007 notes by:
03: P. 17 to 30
Refining a standard for a dual wavelength X-ray diffractometer
03a: P. 31 to 32 Creating a GSAS XRD instrument parameter file using INSTEDIT
Lachlan Cranswick
43Hlachlan.cranswick@nrc.gc.ca
04: P. 31 to 35
Applying an existing GSAS EXP file to a new diffraction data file
Ian Swainson
44Hian.swainson@nrc.gc.ca
05: P. 36 to 40
(File can be freely used and redistributed for

those who wish to learn how to use GSAS
for Rietveld refinement, or adapted to other
Rietveld software. Please keep the above
notice intact.)
Importing a Cif structure file and determining

the polarisation of the X-ray beam using Y2O3
06: P. 41 to 44
Model based Le Bail fitting using GSAS for

pre-structure refinement whole profile fitting
07: P. 45 to 50
True (model-less) Le Bail fitting using GSAS
08: P. 51 to 60
Problems with space group settings and determining the

neutron data wavelength by use of NIST Si 640c;
and modelling a second trace phase
09: P. 61 to 74
Combined Refinement of multiple datasets (X-ray and Neutron)
10: P. 75 to 86
Importing a structure using a GSAS macro file, and

using occupancy constraints and charge balance restraints
11: P. 87 to 93
Quantitative Phase Analysis example using GSAS
12: P. 94 to 95
Applying a QPA GSAS EXP file to a new diffraction file
Workshop sponsored by
45Hhttp://www.uqtr.ca/
46Hhttp://irh.uqtr.ca/
13: P. 96 to 101
Quantitative phase analysis involving preferred orientation
Appendix 1. P. 102:
47Hhttp://www.hydroquebec.co
m/
Additions/corrections
(format of this document based on plagiarising (with permission) the Crystals Single Crystal workshop
notes by Richard Cooper and David Watkin, Chemical Crystallography, Oxford University;
http://www.xtl.ox.ac.uk/ )
48Hhttp://www.cins.ca/
49Hhttp://lansce.lanl.gov/lujan/
SECTION 1
Installing GSAS, EXPGUI and example files
Installing GSAS, EXPGUI

To install GSAS and EXPGUI on an MS-Windows PC:
first download the GSAS and EXP installers from Brian Tobys FTP site at
ftp://ftp.ncnr.nist.gov/pub/cryst/gsas/ (or on the workshop CD in the
\gsas_install\ directory). Run gsas+expgui.exe. Accept all the default
options.
To update GSAS to the latest version, download the GSAS distribution

(gsaskit.exe) from http://www.ccp14.ac.uk/ccp/ccp14/ftpmirror/gsas/public/gsas/ (or on the workshop CD in the \gsas_install\gsas_kits
directory) and extract the files into the install directory. (usually c:\gsas\).
To update to the latest version of EXPGUI, download the latest

expgui_Alpha.zip from ftp://ftp.ncnr.nist.gov/pub/cryst/gsas/ (or on the CD in
the \gsas_install\gsas_kits directory)and extract it into the \gsas\expgui\
directory.
Important: For a Windows system: if the directory depth for the GSAS
installation and/or the data files is too deep, GSAS functions such as Powpref
and Genles may give an error and not run correctly.
The reference to use for GSAS in any resulting publications is: A.C. Larson and R.B.
Von Dreele, "General Structure Analysis System (GSAS)", Los Alamos National
Laboratory Report LAUR 86-748 (1994).
The reference to cite in any resulting publications for using EXPGUI is: B. H. Toby,
EXPGUI, a graphical user interface for GSAS, J. Appl. Cryst. (2001). 34, 210-213
Installing tutorial example files
Extract the cpdw_prac_files.zip file (located in the root directory of the CD-ROM
provided with the tutorial manual) into the c:\cpdw directory of your PC.
They can also be found on the web at http://www.cins.ca/cpdw/files/cpdw.zip
SECTION 2
An Easy start: refining the structure of corundum (Al2O3) powder using diffraction data collected on a
neutron powder diffraction system
Important: Before running your samples, the powder diffractometer should be
aligned as well as possible. If the user of a diffraction system, check the
alignment with suitable standard such as NIST Silicon 640c before running
your samples. If the diffractometer is not well aligned, raise the problems with
those responsible for the equipment and get the system aligned before
continuing. It is easy to invalidate results by running samples on a poorly
aligned and maintained equipment.
As a first (easy) example, we are going to refine on constant wavelength neutron
powder diffraction data. Constant wavelength neutron powder diffraction data can be
easy to fit using conventional Rietveld refinement due to symmetric peak-shapes and
moderately broad peak widths (compared to X-ray systems). This corundum data is
from the C2 neutron powder diffractometer at Canadian Neutron Beam Centre,
National Research Council, Chalk River, Ontario, Canada.
Double click the EXPGUI icon
on the desktop, and the "Select an experiment file
to read" dialog will be displayed. Browse to: c:\cpdw\al2o3_neutron directory, type in
corundum and click READ.
EXPGUI will give a message that the file does not exist. Select the Create button to
create the CORUNDUM.EXP file.
Enter an experimental title Corundum run on C2 NPD at Chalk River and click
"OK" to give the following starting EXPGUI screen.
Adding a Crystal Structure manually into GSAS

Important: Before you can add any histograms (powder diffraction data),
you must first add in a phase (crystal structure) data
Corundum has a Rhombohedral structure. For the convenience to both the GSAS
software (which can only refine rhombohedral structures in the hexagonal setting) the
following structure is in the hexagonal setting with the following crystallographic
details:
Space group: R 3 c
Unit cell: a=b= 4.77 c= 13.02 : alpha=beta=90 gamma = 120
Atom co-ordinates: (x, y, z)
Al :
0
0
0.35
O :
.31
0
0.25
Select the Phase tab and then the Add Phase button. This will bring up an add
new phase dialog where you input the Phase title (Corundum); the Space Group (R
3 c) (make sure to include the spaces) and the unit cell constants. Then select the
Add button. GSAS will then give a symmetry analysis output for you to
check and make sure you have entered the space group correctly (using the
International Tables or similar database to validate the output). Select
Continue once you are happy with this. This will give the following main
EXPGUI screen with the cell information but no atoms.
Now select the Add New Atoms button and add in the atom information using the
keyboard. Select the More atom boxes to add an extra line to insert the Boron atom
information.
Al :
0
0
0.35
O :
.31
0
0.25
Select the Add Atoms button to go back to the main EXPGUI screen where
all the crystallographic information is now visible. The GSAS default values
of Uiso (0.025) are usually too large for inorganic structures. Often it is
better to reset the starting UISO values to 0.01. Change the UISO values
from 0.025 to 0.01 by selecting the UISO values one at a time with the mouse
and changing to 0.01.
Creating a generic GSAS Instrument Parameter file

Important: Before you can add a histogram, you need to create or have an
existing GSAS instrument parameter file ready. Assuming this is the first time
you have used GSAS and you dont have an instrument parameter file for this
single wavelength neutron powder diffractometer, we will now create one.
From the top menu, select Powder, Instedit then the Cancel button to create a new
GSAS Instrument Parameter file. This will bring up the following screen. In the
Data type, select CW Neutron for constant wavelength Neutron.
For title, give Generic prm file for C2 NPD using 531 of Silicon monochromator
and for Instrument Name give C2 531 Silicon Mono. The wavelength is 1.33034 ,
give a zero correction of 7.77 centidegrees (normally this should be a constant of the
diffractometer but if not determined, it can be refined). The zero correction offset for
the diffractometer (which should be a constant), can be determined experimentally for
a diffractometer by running NIST 640c silicon. The manager of the diffractometer
should be able to provide the above information.
At this point DO NOT touch the Import Profile icon or the Add Profile icon. In the
Select Profile area, select Profile type3 (Pseudo-Voight/FCJ Assym). This will
display a number of fields relating to fitting the peak profile (width, shape, asymmetry)
In the profile fields, add a peak cutoff of 0.001 and a GW (constant width) of 400.
In this neutron diffraction example, we do not have to worry about the Finger Cox
Jephcoat (FCJ) peak asymmetry as there is negligible peak asymmetry in this neutron
powder diffractometer.
Now select the Save As button and save the file with a suitable filename; in this case
c2neutron.prm. Then Close Instedit.
Adding a Histogram (diffraction data) into GSAS

Select the Histogram tab followed by the Add Histogram button
To the right of Data File, use the Select File button and add the corun531.gsa
dataset; following by the Select File button to the right of the Instrument Parameter
File to select the c2neutron.prm file. Make sure the Select Bank and Select
Set are set to 1 as pointed to in the screen image to the left of this text. Select the
Add button to add the histogram into GSAS.
Important: If you use a random GSAS instrument parameter file, there are no
guarantees that it contains the correct information and the correct instrumental
settings; and you should check things to make sure it has provided correct
information.
Fitting the background using BKGEDIT

Important: Many people are in the habit of choosing a type of background
function out of habit. In this demonstration, a Shifted Chebyshev (Function 1)
is used and can be very flexible for fitting bumpy backgrounds. Other people
swear by a Cosine Fourier Series (Function 2)
At this point, it would be good to manually fit a background function to the
background in preparation for us starting the refinement. For this we will use the
bkgedit program. Prior to running bkgedit, powpref and genles must be run. Run the
Powpref icon in the top middle menu bar in EXPGUI, followed by GENLES.
After running powpref and genles, run Powder, bkgedit to bring up the background
editing screen. The main aim of this is to select background points by pointing and
clicking with the mouse, then fit a GSAS background function to the data which is then
fixed until you decide to let the background refine. This can save on quite a bit of
tedium trying to immediately refine a GSAS background function at an early stage of
the refinement.
Use the mouse, Add, Zoom and Delete options to visually select background points.
Which below are shown as pink triangles.
Then use the Fit icon to fit a line. Gradually increasing the number of terms until you
get a good fit to the background function. In this case, 6 terms seem to be doing a
good job. The dotted blue line shows the background function.
Now select the Save in EXP File & Exit icon at the bottom right of the screen to
save the fitted background profile. When EXPGUI prompts that the EXP file has been
modified, select the Load new file (unless you have made a mistake). If you have
made a mistake, select the continue with old button. EXPGUI will recognise the
new background parameters by giving the new number of terms you used to fit the
background profile. It is recommended that the background should not be refined until
everything else is pretty much under control.
Getting the best fit to the peak profile

In the Profile tab, make sure the profile type is profile 3 (Pseudo-Voight with FingerCox-Jephcoat peak asymmetry function). It is possible that the instrument parameter
file you used defaults to another profile type, so you should check this. If it is not
profile number 3, then change it to profile type 3. Now run powpref and genles to do
some cycles of refinement with only the scale factor refining.
Now run liveplot (and keep this window open) to see the state of the refinement in
terms of how well the calculated pattern based on the structure model is fitting the
data. By default, the scale factor is set to refine. The black crosses are the raw data;
the red line is the calculated pattern and the blue line below is the difference. The aim
is to get the calculated pattern matching the observed pattern with the difference being
as close to a flat line as possible.
Using the File, Tickmarks option in Liveplot, you can also overlay where HKLs are
expected, and the [Control] [Shift] and left click on the left Mouse button near the
HKL will label the HKL. (To have HKL labels near the peaks, you have to enable the
tickmarks via File, Tickmarks in Liveplot). If you have extra peaks in the raw
diffraction data that are not matched up by a calculated HKL, this can mean you have
the wrong cell or spacegroup, or an impurity phase.
Important: There is no fixed method of performing a Rietveld refinement in

terms of the order of parameters to be released. The following is just a
suggestion, and should not be blindly followed in all cases. Each refinement
may require its own custom refinement sequence for parameters to refine in a
stable manner.
In the LS controls Tab, set the number of cycles to 8 and in the Profile Tab, set the
profile cutoff to 0.001 (if it is not already at 0.001). By default many GSAS
parameter files default to 0.01, which is not adequate for many X-ray and neutron
diffractometers.
Set the unit cell parameter to refine (in the Phase tab) and the Zero parameter to
refine in the Histogram Tab. Performing a refinement on NIST silicon should give you
the zero offset of the diffractometer which should be a constant, however, to get the
best fit to the neutron data using GSAS, it might vary slightly.
If you find that you have mucked up the refinement where parameters have gone to
unreasonable values, it might be easier to go to a previous version of the EXP file. In
EXPGUI, go into File Open menu and then select the Include Archived Files;
this lists the previous archived files by time and date. Just select a previous EXP file
you expect to be OK. If this turns out to be too late or early an EXP file, just try
selecting another one.
Important: Whenever you change the profile cutoff, powpref needs to be run
for this change to take effect in the refinement. (when in doubt, run powpref
prior to running genles). Now run powpref followed by genles
Now run powpref followed by genles. The fit will get slightly better due to the
calculated peaks better lining up with the observed peaks. While the following may
vary depending on your starting peak width and shape values, the a=b unit cell has
changed from 4.77 to around 4.7688; the c unit cell value from 13.02 to 13.0248; with
a zero changed from 7.77 of 9.85.
Important: If after refining unit cell and Zero, the fit looks almost as bad as
when you started, use the mouse to zoom up on a relatively low angle peak in
Liveplot and take a look at the observed vs calculated profiles. In the below
left frame, you can see the red calculated profile is too wide. Resetting the GW
width to half of its value will help get a better starting fit; if that does not work,
try half again. In the initial stages of the refinement, manual tweaking of
starting parameters may be required. Below we see the tweaking of the GW
width value from 400 to 300 to 100 (In the Profile Tab) to give a decent visual
starting fit to the refinement.
10
Now we are going to refine width, shape and peak asymmetry; but it has to be done in
a slow sequence to keep the refinement stable. In the Profile Tab, release the GW
peak width parameter, then run Genles. Initially the fit may only improve marginally.
In the Profile Tab, release the LY shape parameter, then run Genles.
For an X-ray diffraction system, you might next released the GV width parameter.
However, for this neutron diffractometer, it can be best to next release the GU width
parameter. The sequence to release parameters is often found experimentally by trying
things out. In the Profile Tab, release the GU shape parameter, then run Genles.
The width and shape parameters are getting better, but the intensities are moderately
out. In another practical, we will learn on how to do Le Bail whole profile fitting, prior
to structure refinement, which helps solve these initial peak profiling problems. But
for now, the solution is to refine some atomic parameters. This reinforces how on
occasion, the refinement pathway may only be elucidated during the refinement. Some
11
Rietveld guidelines suggest getting the best profile fit to the data before releasing atom
parameters.
If this was X-ray diffraction data, you should slowly release the atoms in reverse order
of atomic number (heavy atoms first). However, the atomic scattering factors in
Neutron diffraction for Aluminium and Oxygen are quite similar, so the atoms can be
released at roughly the same time. In the Phase tab, release the UISO (thermal)
parameters for the Al and O atoms. The Al and O atoms are both on special positions
so are restricted in their movements. E.g., with the Aluminium x and y positions at the
special position of zero, GSAS would still keep these two co-ordinates fixed as
required by the space group. Be wary that other Rietveld programs would move the
atoms on special positions, even if spacegroup does not allow this. When performing a
Rietveld structure refinement a good knowledge of crystallographic fundamentals is
assumed and Rietveld programs can not be used in substitute for crystallographic
knowledge.
If the thermals for atoms do go negative, this could be indicative of problems such as
incorrect atoms having been entered or systematic errors in the data. Also, if the
calculated peak shape near the peak tails are concatenated, run powpref followed by
genles which should fix this up where the intensities now roughly match up over the
length of the powder pattern.
As this data has a wide angular range, now release the LX shape parameter followed
by some cycles of refinement, then release the GU width parameter followed by cycles
of refinement.
12
All of this should give the following decent fit to the whole profile.
Refining the background

Up till now the background has been fixed. Now refine the background via the
Histogram Tab.
Refining the atom positions

Again, if this was X-ray diffraction data, you should slowly release the atoms in
reverse order of atomic number (heavy atoms first). However, the atomic scattering
factors in Neutron diffraction for Aluminium and Oxygen are quite similar, so the
atoms can be released at roughly the same time. In the Phase tab, now release the Xs
for the Al and O atoms and perform some cycles of refinement. If the atoms have
strange negative or very large thermals, this could be telling you that there is
something wonky with the structure model; or systematic errors in the data.
The refinement is pretty much over.
13
Examining the Rietveld plot

Now examine the Rietveld plot, being on the lookout for misfits at low and high
angle, as well as other misfitting peaks and any spurious peaks.
Checking the structure

One of the main validations of a refined structure is to check the bond lengths and
angles to see if they make sense. If new to a phase system and not sure what are
physically reasonable results for certain atom types, the bond lengths and angles from
structures from the relevant structure database can be used as a guide (i.e., the
Inorganic Crystal Structure Database via http://www.fizinformationsdienste.de/en/DB/icsd/ ). To get a list of bond lengths and angles from
GSAS, from the top menu select Results, Disagl.
14
SECTION 2a
Creating a GSAS neutron instrument parameter file using
INSTEDIT
Important: the sample dependent parameters should NOT be incorporated into
the Instrument Parameter file. This means trans (if refined) and shft (if
refined not relevant for neutron cylindrical samples) should be set to zero
after importing the profile information.
Important: Before running your samples, the diffractometer should be aligned
as well as possible. If the user of a diffraction system, check the alignment with
an appropriate standard (NIST Silicon) before running your samples. If the
diffractometer is not well aligned, raise the problems with those responsible for
the diffractometer and get the system aligned before continuing.
Run Powder, Instedit and load the previously created Instrument Parameter file
(c2neutron.prm).
Select the Import Profile button and select the Corundum.exp file; and confirm the
importing of the profile determined from the Corundum refinement you have just
previously performed.
15
Save and overwrite the existing c2neutron.prm with this new updated version of the
instrument parameter file. This instrument parameter file can now serve as the
instrument parameter file for data collected on this same instrument. The trans (if
refined) and shft should be set to zero as these are dependent on the individual
sample, not the instrument. This is not relevant for neutron data in a cylindrical
sample holder, but is for Bragg-Brentano X-ray diffractometers.
16
SECTION 3
Refining NIST CeO2 standard to obtain an instrumental
profile of a dual Cu1+2 wavelength Bragg-Brentano flat
plate X-ray powder diffractometer
Important: the sample dependent parameters should NOT be incorporated into
the Instrument Parameter file. This means trans and shft should be set to
zero after importing the profile information.
Important: Before running your samples, the diffractometer should be aligned
as well as possible. If the user of a diffraction system, check the alignment with
standard (NIST Silicon and NIST LaB6) before running your samples. If the
diffractometer is not well aligned, raise the problems with those responsible for
the laboratory and get the system aligned before continuing. It is easy to
invalidate results by running samples on a poorly aligned diffractometer.
to read" dialog will be displayed. Browse to: c:\cpdw\ceo2newxrd directory, type in
ceo2 and click READ.
create the CEO2.EXP file.
Enter an experimental title CEO2 and click "OK" to give the following starting
EXPGUI screen.
Adding a Crystal Structure manually into GSAS

Important: Before you can add any histograms (powder diffraction data),
you must first add in a phase (crystal structure) data
17
CeO2 is a Cubic structure with the following crystallographic details:

Spacegroup: F M 3 M
Unit cell: a=b=c= 5.410 : alpha=beta=gamma = 90
Atom co-ordinates: (x, y, z)
Ce :
0
0
0
O :
0.25
0.25
0.25
Select the Phase tab and then the Add Phase button. This will bring up an add new
phase dialog where you input the Phase title (CeO2); the Space Group (F M 3 M)
(make sure to include the spaces) and the unit cell constants. Then select the Add
button. GSAS will then give a symmetry analysis output for you to check and make
sure you have entered the spacegroup correctly (using the International Tables or
similar database to validate the output). Select Continue once you are happy with
this. This will give the following main EXPGUI screen with the cell information but
no atoms.
Now select the Add New Atoms button and add in the atom information using the
keyboard. Select the More atom boxes to add an extra line to insert the Boron atom
information.
Ce
0
0
0
O
0.25
0.25
0.25
Select the Add Atoms button to go back to the main EXPGUI screen where all the
crystallographic information is now visible. The GSAS default values of Uiso (0.025)
are usually too large for heavy metal structures. Often it is better to reset the starting
UISO values to 0.01.
18
Creating a starting GSAS Instrument Parameter file

Important: Before you can add a histogram, you need to create or have an
existing GSAS instrument parameter file ready. Assuming this is the first time
you have used GSAS and you dont have an instrument parameter file for this
single wavelength diffractometer, we will now create one.
From the top menu, select Powder, Instedit then the Cancel button to create a new
GSAS Instrument Parameter file. This will bring up the following screen. In the
Data type, select CW X-ray for constant wavelength X-ray.
For title, give Generic prm file for Cuk alpha 1+2 Bragg-Brentano
Diffractometer and for Instrument Name give cukal1_2. The radiation type is Cu,
it is monochromatic (dual wavelength), give a zero correction of -0.07 centidegrees
(Zero correction offset for the diffractometer, which should be a constant, as distinct to
the sample displacement error, can be determined for a diffractometer by running NIST
640c silicon). A POLA value of 0.911. ( IPOLA should be set to 1 which defines the
use of the Azaroff function, but currently there is not an option to do this in the Instedit
screen, so it needs to be set in the EXP file during refinement). Paraphrasing a note
from Bob von Dreele, IPOLA=1 is in there to match the "traditional" Azaroff
function for diffracted beam monochromators. The IPOLA=0 function is my adaption
so that POLA is the polarized fraction. POLA=0.50 for no polarization and POLA=1.0
for perfect polarization nearly realized in synchrotron radiation & vertical
diffraction.. Polarization fraction can be calculated, but it can be good to determine
this experimentally by running a suitable phase such as cubic Y2O3 from the lowest to
highest angle of the diffractometer e.g., 5 to 150 degrees 2-theta).
In the Select Profile area, select Profile type3 (Pseudo-Voight/FCJ Assym), with a
peak cutoff of 0.001 and a GW (constant width) of 400. The Finger Cox Jephcoat
(FCJ) peak asymmetry is defined by two parameters, S/L and D/L, where S/L is the
source size to sample-detector distance ratio and D/L is the detector size to sample-
19
detector distance ratio, as per the following figure taken from L. W. Finger, D. E. Cox
and A. P. Jephcoat, A correction for powder diffraction peak asymmetry due to axial
divergence, J. Appl. Cryst. (1994). 27, 892-900.
It is best if you calculated these values from measuring these values on the
diffractometer. If you received the data from someone else and cannot get these
diffactometer values, take a best guess (e.g., for this type of medium resolution
diffractometer, 173mm for sample-detector distance and 5mm for source size and
detector size. This gives starting S/L and D/L ratios of 0.029.
Now select the Save As button and save the file with a suitable filename; in this case
cuka12xrd.prm. Then Close Instedit.
Adding a Histogram (diffraction data) into GSAS

Select the Histogram tab followed by the Add Histogram button
To the right of Data File, use the Select File button and add the
ceo2newxrd.gsa dataset; following by the Select File button to the right of the
Instrument Parameter File to select the cuka12xrd.prm file. Make sure the
Select Bank and Select Set are set to 1 as pointed to in the screen image to the left
of this text. Select the Add button to add the histogram into GSAS.
20
In the above screen image, if the Ratio of the wavelengths is at zero instead of 0.5, set
the Ratio to 0.5 (the correct value). As POLA is set at a value for a curved graphite
diffracted beam monochromator based on using the Azaroff function (0.911), IPOLA
should be set to 1 to get GSAS to use the Azaroff function.
Important: If you use a random GSAS instrument parameter file (or even one
that looks correct), there are no guarantees that it will import the correct
information and the correct instrumental settings; and you should check things
to make sure it has provided correct information.

Important: Many people are in the habit of choosing a type of background
function out of habit. In this demonstration, a Shifted Chebyshev (Function 1)
is used and can be very flexible for fitting bumpy backgrounds. Other people
swear by a Cosine Fourier Series (Function 2)
At this point, it would be good to manually fit a background function to the
background in preparation for us starting the refinement. For this we will use the
bkgedit program. Prior to running bkgedit, powpref and genles must be run. Run the
Powpref icon in the top middle menu bar in EXPGUI, followed by GENLES.
After running powpref and genles, run Powder, bkgedit to bring up the background
editing screen. The main aim of this is to select background points by pointing and
clicking with the mouse, then fit a GSAS background function to the data which is then
fixed until you decide to let the background refine. This can save on quite a bit of
tedium trying to immediately refine a GSAS background function at an early stage of
the refinement.
Use the mouse, Add, Zoom and Delete options to visually select background points.
Which below are shown as pink triangles.
21
Then use the Fit icon to fit a line, gradually increasing the number of terms until you
get a good fit to the background function. In this case, 6 terms seem to be doing a
good job. The dotted blue line shows the background function.
Now select the Save in EXP File & Exit icon at the bottom right of the screen to
save the fitted background profile. When EXPGUI prompts that the EXP file has been
modified, select the Load new file (unless you have made a mistake). If you have
made a mistake, select the continue with old button. EXPGUI will recognise the
new background parameters by giving the new number of terms you used to fit the
background profile. It is recommended that the background should not be refined until
everything else is pretty much under control.
22

In the Profile tab, make sure the profile type is profile 3 (Pseudo-Voight with FingerCox-Jephcoat peak asymmetry function). It is possible that the instrument parameter
file you used defaults to another profile type, so you should check this. If it is not, then
change it to profile type 3. Now run powpref and genles to do some cycles of
refinement with only the scale factor refinining.
Now run liveplot (and keep this window open) to see the state of the refinement in
terms of how well the calculated pattern based on the structure model is fitting the
data. By default, the scale factor is set to refine. The black crosses are the raw data;
the red line is the calculated pattern and the blue line below is the difference. The aim
is to get the calculated pattern matching the observed pattern with the difference being
as close to a flat line as possible.
Using the File, Tickmarks option in Liveplot, you can also overlay where HKLs are
expected, and the [Control] [Shift] and left click on the left Mouse button near the
HKL will label the HKL. (To have HKL labels near the peaks, you have to enable the
tickmarks via File, Tickmarks in Liveplot). If you have extra peaks in the raw
diffraction data that are not matched up by a calculated HKL, this can mean you have
the wrong cell or spacegroup, or an impurity phase.
Important: There is no fixed method of performing a Rietveld refinement in

terms of the order of parameters to be released. The following is just a
suggestion, and should not be blindly followed in all cases. Each refinement
may require its own custom refinement sequence for parameters to refine in a
stable manner.
Also, if you find that you have mucked up the refinement where parameters have gone
to unreasonable values, it might be easier to go to a previous version of the EXP file.
In EXPGUI, go into File Open menu and then select the Include Archived Files;
this lists the previous archived files by time and date. Just select a previous EXP file
you expect to be OK. If this turns out to be too late or early an EXP file, just try
selecting another one.
23
In the LS controls Tab, set the number of cycles to 8 and in the Profile Tab, set the
profile cutoff to 0.001 (if it is not already at 0.001). By default many GSAS parameter
files default to 0.01, which is not adequate for many X-ray diffractometers.
Important: Whenever you change the profile cutoff, powpref needs to be run
for this change to take effect in the refinement. (when in doubt, run powpref
prior to running genles). Now run powpref followed by genles
Important: If after refining the scale factor, the fit looks very bad, it is best to
evaluate what is going on and base your refinement strategy on this. If the
observed peaks do not match up with the calculated, this could be telling you
your unit cell needs to be tweaked manually or you have the wrong unit cell or
spacegroup.
In the below left frame, you can see the red calculated profile is too wide. So it
is best to manually adjust the width before releasing any further parameters.
Resetting the GW width to half of its value will help get a better starting fit; if
that does not work, try half again. In the initial stages of the refinement,
manual tweaking of starting parameters may be required. Below we see the
tweaking of the GW width value (In the Profile Tab) to give a decent visual
starting fit to the refinement. In the following we have had to do a lot of
interations, eventually going down to a GW of 10.
24
Now that we have got the peak width in roughly the right range, set the unit cell
parameter to refine (in the Phase tab) and the shft parameter to refine in the Profile Tab
(shft = sample displacement). For a Bragg-Brentano diffractometer, it is better to use
the shft parameter over the zero parameter as most of the variation in an aligned
diffractometer is due to accurate placement of the sample. Performing a refinement on
NIST silicon should give you the zero offset of the diffractometer which should be a
constant.
Now run powpref followed by genles. The fit will get better due to the calculated
peaks better lining up with the observed peaks. While the following may vary
depending on your starting peak width and shape values, the unit cell has changed from
5.4100 to around 5.4108, with a sample displacement value of -0.664E+01. The
following screen images show the level of improvement.
Now we are going to refine width, shape and peak asymmetry; but it has to be done in
a slow sequence to keep the refinement stable. In the Profile Tab, release the GW
peak width parameter, then run Genles. Initially the fit may only improve marginally.
In the Profile Tab, release the LY shape parameter, then run Genles.
25
In the Profile Tab, release the GV shape parameter, then run Genles.
The width and shape parameters are getting better, but the intensities are out. In
another practical, we will learn on how to do Le Bail whole profile fitting, prior to
structure refinement, which helps solve these initial peak profiling problems. But for
now, the solution is to refine some atomic parameters. This reinforces how on
occasion, the refinement pathway may only be elucidated during the refinement. Some
Rietveld guidelines suggest getting the best profile fit to the data before releasing atom
parameters.
In the Phase tab, release the U (thermal) parameter for the heavy Ce atom (not the
light Oxygen atom). The Ce is on a special position so cannot move, but even if you
tried to refine the Ce x,y,z, GSAS would still keep it fixed as required by the space
group. Be wary that other Rietveld programs would move the special position atoms,
even if spacegroup does not allow this. When performing a Rietveld structure
refinement a good knowledge of crystallographic fundamentals is assumed and
Rietveld programs can not be used in substitute for crystallographic knowledge.
If the thermal for the heavy atom of a standard material does go negative, this
could be indicative of problems such as the polarization of the X-ray beam being
incorrect or the wrong atom type. Also, if the peak shape is concatenated, run
powpref followed by genles which should fix this up where the intensities now
roughly match up over the length of the powder pattern.
26
As this data has a very wide angular range, now release the LX shape parameter
followed by some cycles of refinement, then release the GU width parameter followed
by cycles of refinement.
Via the Profile tab, now release the trns (sample transparency parameter) which is
relevant for Bragg-Brentano flat plate systems.
This should give the following decent fit to the whole profile.
27

Up till now the background has been fixed. Now refine the background via the
Histogram Tab.
Refining the atom positions and thermals

When performing a refinement using X-ray diffraction data, you should slowly release
the atoms in reverse order of atomic number (heavy atoms first). In the Phase tab, now
release the Us for the oxygen atom and perform some cycles of refinement (the
Oxygen is on a special position, so there is no point trying to refine the Xs / atom coordinates). Pay careful attention to the thermal parameter of the oxygen. If the light
atoms have strange negative or very large thermals, this could be telling you that there
is something wonky with the data; either bad sample packing, or something wrong
with the diffractometer.
The refinement is pretty much over. One more thing that is possible is to tweak the
H/L and S/L peak asymmetry parameters. These parameters are unstable if refined
together, so first refine one and turn it off, then the other and turn it off, then repeat the
sequence until the refinement converges and (via Liveplot) you see the best fit with the
low angle peaks.
28
Examining the Rietveld plot

The fit to the lowest angle peaks seems to be OK. Though often such things
can be in the eye of the beholder. It can be good to run some NIST standards
on a variety of diffraction systems to get a feel for what fits are possible on
various instruments.
The very high angle peaks also seem OK.
Checking the structure

One of the main validations of a refined structure is to check the bond lengths and
angles to see if they make sense. If new to a phase system and not sure what are
physically reasonable results for certain atom types, the bond lengths and angles from
structures from the relevant structure database can be used as a guide (i.e., the
Inorganic Crystal Structure Database). To get a list of bond lengths and angles from
GSAS, from the top menu select Results, Disagl.
29
30
SECTION 3a
Creating a GSAS Instrument Parameter file from a refined
standard
Run Powder, Instedit and load the previously created Instrument Parameter file
(cuka12xrd.prm).
Select the Import Profile button and select the CeO2.exp file; and confirm the
importing of the profile determined from the CeO2 refinement you have just
previously performed. The trans and shft should be set to zero as these are
dependent on the individual sample, not the instrument. Overwrite the existing
cuka1xrd.prm with this version with the updated information. This instrument
parameter file can now serve as the instrument parameter file for data collected on this
same instrument.
31
SECTION 4
Applying an existing GSAS EXP file to a new diffraction
file
Using the Windows explorer (or your favourite file manager), copy the CEO2.EXP and
cuka12xrd.prm from the \cpdw\ceo2newxrd directory to the \cpdw\ceo2oldxrd
directory.
Either double click on the ceo2.exp file to automatically open it in EXPGUI, or run
EXPGUI and load the cpdw\ceo2oldxrd\ceo2.exp file
Replacing a powder histogram (diffraction data file)

At present, replacing histogram files is done via the EXPEDT program (the
comprehensive GSAS EXP file editor by Bob von Dreele and Allen Larson). Select
the EXPEDT ICON from the top left menu.
Then to get to the point where you can replace the histogram, type K P H R 1 (note
the descriptors within EXPEDT which explain what these mean while you are doing
this). When prompted with Enter raw histogram input file name (<?>,$,QUIT),
type the name of the data file: ceo2oldxrd.gsa and when prompted, confirm this is
correct by typing Y. When prompted with Enter POWDER instrument parameter
file name (<?>,$,QUIT), type the name of the GSAS instrument parameter file:
cuka12xrd.prm and when prompted, choose scan number 1. Dont bother
previewing it. Then type T (Set max 2-Theta or Energy or min TOF), and then / to
confirm the maximum angle is acceptable. To exist EXPEDT, type X X X and
[RETURN], the X and [RETURN].
Check the EXP file is OK, especially in the Histogram tab as some of the Instrument
parameters may not have been imported correctly. Referring to the following screen
image, if the Ratio of the wavelengths is at zero, set this to 0.5. Reset the Ratio to 0.5
(the correct value). As POLA is set at a value for a curved graphite diffracted beam
monochromator based on using the Azaroff function (0.911), IPOLA should be set to
1 to get GSAS to use the Azaroff function. Correct these. This data was actually
32
taken on an older diffractometer (though pretty much identical in setup and

configuration), so it can be expected the Zero will be different. We will probably
work on this later in the refinement.
The new dataset has pretty much the same counting statistics of its replacement. So it
can be pretty much refined in one step using all the parameters. If it had very different
counting statistics, it would be best to do the refinement slowly as per the previous
practicals by turning off all the parameters and turning them back on in a similar
sequence. Though two things to turned off are S/L and H/L as these parameters can
be very unstable.
Now run powpref followed by genles. The refinement is done! Now you should
check things out and see if anything needs tweaking of there have been any problems
doing a refinement as quickly as this may have caused; validate the structure using
disang; and check if there are some nuances or problems with the data file that might
only be revealed in a post refinement examination.
33
Risks of releasing too many parameters

Be wary on just releasing parameters willy nilly without regard to the physical
reality of the sample and possible consequences. Normally, you should not have to
refine trns (sample transparency) with a heavy metal inorganic phase like CeO2.
Though in this example this is what we have done, blindly. Releasing parameters
inappropriately may hide systematic errors in the data and also skew the final results.
Releasing the trns (sample transparency)

If we release the sample transparency parameter, the high angle reflections look OK.
Though both fits seem to be having minor problems.
Old B-B Diffractometer (left) vs new B-B diffractometer (right)

Diffractometer
Uiso*100 Ce
Uiso*100 O
Unit cell
Old
0.24(2)
0.68(13)
5.41253(3)
New
0.16(1)
0.77(7)
5.41004(2)
NIST Certificate*
5.4111(1)
(* http://ois.nist.gov/srmcatalog/certificates/view_cert2gif.cfm?certificate=674a )
Not releasing the trns (sample transparency)

However, if you do not release the sample transparency parameter (keep it at zero), and
look closely at the high angle fit of the old Bragg-Bretano diffractometer
compared to the new Bragg-Bretano diffractometer, you can see problems with
the high angle fit. The old diffractometer was based on stepper motors and had a
retrofit of a diffracted beam curved graphite monochromator. It looks like the updated
anti-backlash springs are not strong enough to take the extra weight; or there are some
other goniometer problems. The new diffractometer theta and 2-theta axes were driven
by DC motors guided by direct drive optical encoders.
Old B-B Diffractometer (left) vs new B-B diffractometer (right)
34
Diffractometer
Uiso*100 Ce
Uiso*100 O
Unit cell
Old
0.30(2)
0.79(13)
5.41311(2)
New
0.15(1)
0.73(8)
5.41062(2)
NIST Certificate*
5.4111(1)
(* http://ois.nist.gov/srmcatalog/certificates/view_cert2gif.cfm?certificate=674a )
The ESDs given by Rietveld analysis are only indicators of probable error assuming
there are no systematic errors. Systematic errors or over simplifications in the model
can make the ESDs meaningless in terms of probable error. With X-ray data,
thermal parameters are well known as sinks for many types of systematic errors in the
peak intensities. For the unit cell discrepancies, errors due to temperature of the data
collection, misalignment of the sample and diffractometer are most likely. To get an
indicator of probable error due to the diffractometer and sample packing, it can be
more sensible to run the same sample with multiple packings, multiple times on
different instruments to get a Standard Deviation, as well as running the sample with
an internal position standard such as NIST Silicon 640c.
Spurious peaks: in this case Cuk and Tungsten

If you look closely at the background, you will notice some peaks that do not have
calculated HKLs. This could imply impurity phases; but in this case is Cuk satellite
reflections from the most intense CeO2 Cuk reflections; in this case the 111 and 220
respectively in the left plot from the newer diffractometer. In the older diffractometer
(right plot), it is more difficult to see as the counting stats are less, and Tungsten
contamination from the (possible older?) X-ray tube is also visible.
35
SECTION 5
Importing a Cif structure file and determining the
polarisation of the X-ray beam using Y2O3
The aim of this section is to show how i) easy it is to import an existing structure file
into GSAS (minimizing the risk of typographical errors) and ii) refining the
polarisation of the X-ray beam. Normally to refine the polarisation of the X-ray bean,
you need to use a standard of decent peak density, and the entire range of the
diffractometer up to the highest angle possible (between 140 to 150 degrees 2-theta).
But be wary that after importing an existing structure, you still need to check that the
structure from the literature is OK and kosher before starting the refinement.
to read" dialog will be displayed. Browse to: c:\cpdw\y2o3_pola directory, type in
Y2O3 and click READ.
create the Y2O3.EXP file and add the title.
Under the Phase tab, click on the Add Phase button, but instead of inputting all the
information by hand, use the Import Phase From button and select Crystallographic
Information File (CIF).
Then select and import the y2o3_icsd_26190.cif file in the c:\cpdw\y2o3_pola

directory. EXPGUI will give a warning that the I a 3 setting of the I a 3 space group
is unlikely to be understood.
Change I a 3 to I a 3. Under more complicated circumstances, the space group and

structure may have to be changed or transformed to a setting that GSAS does
understand.
36
Press Continue. GSAS will output the spacegroup information which you can check
with the IUCr International Tables or other suitable spacegroup database.
This brings up the Adding Atoms dialogue box. Some CIFS can have blank input for
the Uiso values. If they do, has some default values like 0.01. The following values of
zero will be OK, and we will be refining these.
Select Add Atoms to finish importing the structure into GSAS.
37
Now add the histogram as done in previous sections. The datafile is c:\cpdw\
y2o3_pola\ y2o3.gsa and the instrument parameter file is c:\cpdw\ y2o3_pola\
cuka12xrd.prm. If required, correct any problems such as the ratio not being correct
(it should be 0.5). IPOLA should be set to 1 which defines the use of the Azaroff
function. Note the existing value of POLA has been set to 0.81, the theoretical value
of the polarisation correction using the Azaroff function for a curved graphite
monochromator with CukAlpha X-rays. This is the parameter we will eventually be
refining to get a better value. Paraphrasing a note from Bob von Dreele, IPOLA=1 is
in there to match the "traditional" Azaroff function for diffracted beam
monochromators. The IPOLA=0 function is my adaption so that POLA is the polarized
fraction. POLA=0.50 for no polarization and POLA=1.0 for perfect polarization
nearly realized in synchrotron radiation & vertical diffraction. A cos22 of the 002
graphite reflection (For Cu X-rays this is at an angle of 26.6 degrees 2-theta /
d=3.3480) gives a calculated POLA value of around 0.81.
Now set the number of cycles to 8, check the profile cutoff is 0.001, fit the
background and refine the profile, background and structure as per the previous
sections. This should leave you with the following fit.
38
Dont forget to validate the refined structure by using disang to check the refined
structure makes physical sense.
In the Histogram tab, now refine the POLA parameter (which was set at its theoretical
Azaroff function value of 0.81). If you reset the values of the thermal parameters and
reset POLA to different values, it should still converge onto the same value of near
0.90(1), showing the refinement of this parameter is robust.
As there are correlations between parameters such Uiso, and POLA, it can be a good
idea to check the Correlation Matrix is the LSTVIEW output, as it is possible that
correlations are excessive and affecting the accuracy of the result. It can also indicate
39
where due care is required as parameters may be unexpected correlated. In the LS

Controls tab, click on the Print Options Icon and select Print correlation matrix (2).
Now run Powpref and Genles for these new listing options to take effect. Viewing the
output via LSTVIEW will show which parameters have a correlation greater than 0.5.
HSCL is the Histogram Scale factor; PF are profile parameters and BK are
background parameters.
40
SECTION 6
Model based Le Bail fitting using GSAS for pre-structure
refinement fitting
Before using any of the atomic information, it can be convenient to do a structureless
Le Bail fit to the data and get the best whole profile fit before proceeding on to refine
the atomic positions. GSAS has two options, a model biased Le Bail fit, and a true Le
Bail fit. For getting a good fit prior to structure refinement, it can be more convenient
to use the model biased Le Bail fit. This avoids the tediousness of having all the
reflections set to zero after running powpref as with the true Le Bail fitting. The
following Calcium Niobium Oxide example has over 100 atoms (depending on which
model is used, (L.M.D. Cranswick, W.G. Mumme, I.E. Grey, R.S. Roth, P. Bordet, A new octahedral
tilt system in the perovskite phase Ca3Nb2O8, Journal of Solid State Chemistry, 172 (1): 178-187 April
2003)) and it is more convenient to fit the whole profile before trying to sort out the
structural refinement problems. In reality, this was done via a combined refinement
using both X-ray data to lock down the heavy atoms, and neutron data to lock down
the light oxygen atoms. The atom list given with this example is not 100% correct,
which is why refinement of the structure is required.
Important: If you find the following dataset refines to slowly on your PC, you
can do the same tutorial using the Y2O3 data and CIF file.
Because we are going to use an Instrument parameter file with the starting profile
values determined from refining the CeO2 standard, this should be a moderately
painless profile fitting exercise.
Important: Whenever you run powpref while in Le Bail mode, this resets the
HKL intensities. This can mean that you need to fix the profile parameters
while you run a few cycles of Genles to get the intensities roughly matching the
diffraction data, then start releasing profile parameters again.
to read" dialog will be displayed. Browse to: c:\cpdw\lebail_model directory, type in
CANBO and click READ followed, when prompted, by Create to create a new EXP
file. Put in the extra title information as required.
Rather than type in the positions of over 100 atoms manually, we will import the
structure from a CIF file as per the previous example on this topic. Use the
c:\cpdw\lebail_model\starting_canbo_structure.cif file.
41
Now add in the diffraction data/histogram. c:\cpdw\lebail_model\canbo-v.gsa is the

diffraction data file (a variable count time dataset converted into the GSAS ESD
format) and c:\cpdw\lebail_model\cuka12xrd.prm is the instrument parameter file.
As usual, fix up any problems with the Ratio of the wavelengths (0.5). As POLA is
set at a value for a curved graphite diffracted beam monochromator based on using the
Azaroff function (0.911), IPOLA should be set to 1 to get GSAS to use the Azaroff
function. (1).
Run Powpref and Genles, then fit the background graphically using Powder, Bkgedit
as per previous sections.
42
In the LS Controls tab, now enable the F(calc) Weighted button. And turn off the
Scale Factor, which is meaningless to refine during a Le Bail fit as all the HKL
intensities are free to go to whatever value it takes to get the best fit to the data.
Fixing the Scale Factors

Via the Scaling tab, turn off the Scale parameter refinement flags for the X-ray and
Neutron data. (These are turned back on after the Le Bail fitting) Now run Powpref
once, the Genles a few times to get calculated intensities into the observed peaks. As
this is a large cell, this could take a while. You should get a starting fit similar to the
following.
Now slowly release the unit cell, shft, and other profile parameters as per the previous
sections. If the refinement goes unstable, you may have to run powpref again to reset
the Le Bail intensities.
After refining the unit cell and shft, it should look something like the following.
43
After refining the profile parameters, it should look similar to the following.
Now you can turn off all the profile and unit cell parameters and turn back on the
Rietveld refinement to try and get a good initial fit of the trial structure to the data.
Remember to turn back on the Scale Factor.
Run powpref and run genles to start refining the structure. Though you may like to go
to the next exercise. It took around 6 to 12 months to solve this structure, then around
2 years to refine it to completion, from whence it could be published. While the X-ray
data may look like it has a decent fit at the moment, including the neutron diffraction
data was very important to reliably refine the oxygen positions, and work out problems
with the model. The starting neutron fit is included below with the corresponding
starting X-ray fit.
44
SECTION 7
True (model-less) Le Bail fitting using GSAS for structure
solution
If you know the cell and space group but not the structure, you can obtain a set of
intensities from powder diffraction data for structure solution by using Le Bail fitting.
Using model-less Le Bail fitting, all the intensities are set to zero prior to the start of
the fitting procedure, and thus are un-biased by any atoms you may have put in the unit
cell.
Important: If you find the following dataset refines to slowly on your PC, you
can do the same tutorial using the Y2O3 data and CIF file.
Important: Whenever you run powpref while in true Le Bail mode, this resets
the HKL intensities to zero. This can mean that you need to fix the profile
parameters while you run a few cycles of Genles to get the intensities roughly
matching the diffraction data, then start releasing profile parameters again.
For this example, we will use a synchrotron dataset of tetracycline hydrochloride from
the 1st Structure Solution from Powder Diffractometry Round Robin (SDPDRR,
http://sdpd.univ-lemans.fr/SDPDRR/ ). The instrument profile were not provided with
the data from the synchrotron, so you will have to slowly fit the peak profile
parameters as part of the Le Bail process. If you obtain data from a third party, it
would save some tedium if you could also obtain a good instrument parameter file of
the diffractometer. You will have to create a starting instrument parameter file for this
example.
Important: This data was collected from a capillary, thus parameters relevant
to flat plate Bragg-Brentano instruments (trns and shft) should not be used. The
Refine Zero in the Histogram Tab should be used.
Wavelength = 0.692 Angstrom; Polarisation of the X-ray beam (IPOLA=0) of

1.
The orthorhombic spacegroup of tetracycline hydrochloride is P 21 21 21
The unitcell of tetracycline hydrochloride is 10.981 12.853 15.733 90 90 90

to read" dialog will be displayed. Browse to: c:\cpdw\lebail_modeless directory, type
in tetcy and click READ followed, when prompted, by Create to create a new EXP
file. Put in the extra title information as required.
Then via the Phases tab, add a new phase with the above parameters.
45
Important: When adding a cell and spacegroup, GSAS still needs one atom for
it to run Genles, even when doing structureless Le Bail fitting. Thus to keep
GSAS happy, a dummy atom needs to be added.
Thus as per the above, add a dummy Hydrogen atom at 0 0 0.
Now create a default Instrument parameter file for this synchrotron data file using
Powder Instedt. Give a title similar to Daresbury 9.1 in image plate mode at 0.692
Angstrom and an Instrument name of something like Daresbury 9.1. It is a
constant wavelength X-ray instrument with radiation type of Other. The wavelength
is 0.692 and the polarisation fraction is 1. As this is synchrotron data with good
resolution, give the GW parameter a value of 2. Then Save As to save the file with the
name synca.prm.
Now in the Histogram tab, add the diffraction data file (ALDSYNC.gsa) and
instrument parameter file (synca.prm)
46
In the Scaling tab, turn off the Scale Factor and in the L S Controls tab, enable Equally
Weighed (Le Bail method).
Now run powpref and then genles. Then view the plot in Liveplot.
As the very low angle data (where there are no Bragg peaks) has a strange background
which would be tedious to try and fit a function to, and there are hardly any reflections
above 36 degrees, we are going to exclude these areas. Now run the Powder, Excledt
program. Using the Add Region ICON and the click and drag with the mouse to add
the two excluded areas at the extreme ends of the data. When completed, click Save
and Finish. Then run Powpref (so this change takes effect) and genles.
47
Making sure you have run Powpref and genles after excluding the lower and upper
angle regions, now run Powder, Bkgedit to manually fit a background function to the
data. Because a glass capillary was used to hold the powder sample, the background
has humps in the data that need to be fitted as part of the background function. In the
following screen image, a 18 term function seems to be doing the job. Click on Save
in EXP file & Exit to continue on.
Now run powpref (which resets the Le Bail intensities to zero). Then run genles
twice. It will normally take running genles twice to get a decent about of intensity into
the peaks, as the following two screen images show. Genles will only do one cycle
each time as no parameters have been set to refine at this point.
(Left: first run of genles; Right: second run of genles)
48
Now refine the Unit Cell and Zero where you should get the following style of fit.
Continue on as with the previous sections for refining the profile parameters. Though
remember to NOT release shft or trns. Use you best judgement to how many
parameters need to be released, and whether the peak asymmetry parameters S/L and
H/L need to be released. At some point, you will most likely have to release the
background to refine. Be very careful when doing this with Le Bail fitting.
If you see evidence of peak concatenation, you may have to change the peak cutoff (in
the Profile tab) to 0.0001. If you do this, turn off ALL the refined parameters
(including the background), run powpref, run genles 2 to 4 times, then turn the
parameters back on. If you do not turn off all the parameters, the parameters that
have been left to refine will go tend to go completely beserk.
(with peak concatenation with peak cut-off at 0.001)
(setting the peak cut-off at 0.0001)
49
After refining the 3 width and 2 shape parameters (with background, zero and unit
cell), you should be at the following point in the Le Bail fit.
You can now use Results, Reflist to export the list of HKL and intensities. After some
minor sorting and reediting, these can be passed into favourite HKL based structure
solution software in an attempt to solve the structure.
50
SECTION 8
Problems with space group settings and determining the
neutron data wavelength by use of NIST Si 640; and
modelling a second trace phase.
The aim of this section is to show how i) easy it is to import an existing structure file
into GSAS (minimizing the risk of typographical errors); ii) recognize problems with
the imported structure, including the space-group setting and iii) refining the value of
the wavelength by the use of a NIST Si 640c standard. Note that if there are not
enough reflections to refine the wavelength, mixing in a phase like annealed cubic
Y2O3 can allow the wavelength to be refined as the Y2O3 add more observations for the
refinement of the zero offset. This data was taken from the 5 3 1 reflection of a Silicon
monochromator at a take-off angle of -92.732, which will result in a wavelength of
around 1.33.
to read" dialog will be displayed. Browse to: c:\cpdw\silicon_neutron directory, type
in silicon and click READ.
create the SILICON.EXP file and add the title.
Under the Phase tab, click on the Add Phase button, but instead of inputting all the
information by hand, use the Import Phase From button and select Crystallographic
Information File (CIF).
Then select and import the si_icsd_51688.cif file in the c:\cpdw\silicon_neutron

directory. EXPGUI will give a warning that the F d -3 m S is unlikely to be
understood, as GSAS only understands standard Hermann-Maugin space group
symbols.
Change F d -3 m S to F d -3 m Under more complicated circumstances, the space

group and structure may have to be changed or transformed to a setting that GSAS
does understand.
51
Press Continue. GSAS will output the spacegroup information which you can check
with the IUCr International Tables or other suitable spacegroup database.
This brings up the Adding Atoms dialogue box.
GSAS will complain if the Atom Type of Si (neutron atom) has its charge labelled
as Si0+. Change this to Si. Some CIFS can have either blank input or have Biso
values instead of the GSAS required Uiso values. In this case, there is a Biso value
present in the structure information. Biso = 82Uiso : Uiso = Biso/78.96. So just this
formula to convert the Biso to Uiso values: a Biso of 0.54 becomes a Uiso of 0.0068.
52
Now add the histogram as done in previous sections. The datafile is c:\cpdw\
silicon_neutron\ si_531.gsa and the instrument parameter file is c:\cpdw\
silicon_neutron\ c2neutron.prm.
Now set the number of cycles to 8; and check the profile cutoff is 0.001. Run
Powpref and Genles and fit the background.
53
Set the unit cell for NIST 640c Silicon at its certificate value of (when measured at
22.5C - https://srmors.nist.gov/view_cert.cfm?srm=640C ) of 5.4311946. This is
done by going to the Phase Tab and selecting Edit Cell icon.
Now refine, via the Histogram Tab, refine the Wavelength and Zero offset (the unit
cell of Silicon remains FIXED at its NIST value). As you have changed the unit cell
manually, run Powpref followed by Genles.
As per the following screen image, the fit is very woeful given this is a standard
material with a single atom located on a special position. (The peak at 52 where there
is no calculated HKL is a Vanadium peak from the Vanadium sample can).
54
To cut a long story shorter, if you have not encountered this problem before, it is easy
to waste a lot of time trying to figure out what is going on. Is this really the correct
sample? Was the correct wavelength set? Some strange bug in the program?
Occupancies, thermal and position correct? Is it possible that severe preferred
orientation/texture will be reponsible for this? (in the case of Silicon powder:
not bloody likely) The solution to this is the default space-group setting used by
GSAS. GSAS assumes the a setting of the F d 3 m space group which has the Origin
at 0,0,0. However, if you look up F d 3 m (No 227) in the IUCr International Tables
Vol A, it puts the Origin at 1/8, 1/8, 1/8. So if you translate the Silicon atom to 1/8,
1/8, 1/8 (0.125, 0.125, 0.125) the calculated pattern will probably start fitting the
observed much better.
As another check, if you look inside the Silicon CIF file with a text editor, it includes
the Wyckoff position for the Silicon atom: 8a. In the International Tables, 8a is the
1/8, 1/8, 1/8 position.
As another, another check, if you run the GSAS DISAGL program (via Results,
Disagl), when Silicon is located at 1/8, 1/8, 1/8, all the Si to Si bond distances are
2.352 with Si-Si-Si bond angles of 109.47. If you put the Si at 0, 0, 0, then the bond
distance is 1.92 and the bond angles are all over the place in a manner that would be
unexpected for a diamond structure type.
In the Phases Tab, click on the Silicon atom line, then in the bottom details box,
change 0 to 0.125 for X Y and Z.
55
Run Powpref and Genles. This gives a much better fit as per the following screen
image.
Now, as with previous examples, complete the refinement by fitting the profile,
refining the background and releasing the silicon thermal/Uiso parameter.
To record the wavelength, Zero and ESDs, open LSTVIEW (ICON 2nd from the right
on the top EXPGUI program bar) and scroll down to the bottom to find the
C/L1/R/2Th (wavelength) and Zero.
56
It is not good practise to have an impurity phase un-modelled in the Rietveld analysis.
Thus, similar to before, now add in the Vanadium phase and finish off the refinement.
The Vanadium structure is given in the vanadium_icsd_52537.cif file in the
c:\cpdw\silicon_neutron directory. As the Vanadium peaks are present in trace
amounts, we will most likely have to constrain the thermals and profile values to be
equal to the major phase.
In the Phases Tab, import the vanadium_icsd_52537.cif file. Change V0+ to V
and give the Vanadium thermal/Uiso the same as the Silicon (this can be
changed later in the Phases Tab (phase 2 ICON) for the Vanadium)
The scale factors for the two phases have to refine separately. Thus to into the Scaling
Tab and fix the overall scale factor, and refine the individual phase fraction scale
factors (as shown in the following screen image).
If you have a LivePlot window already open, close it as the HKLs for the new
Vanadium phase will not be displayed. Run Powpref (to generate the HKLs for
Silicon and Vanadium) then run Genles.
Open LivePlot and zoom up to the background. Display the HKLs for the Vanadium
via the Liveplot menu (File, Tickmarks, Phase 2 ; and Option, Configure Tickmarks,
Manual Placement). In the following screen image, it is easy to see that the intensities
for the Vanadium metal are not matching up.
57
As this is a metal can, it can very likely be suffering from very severe texture/preferred
orientation. But first, we had better check the International Tables Vol A information
on I M 3 M (No 229) and make sure we have the space group setting correct for
Vanadium. It is easy to get confused here as if the Vanadium does have very severe
preferred orientation (which would be expected), it could be that putting the Vanadium
atom into another site (using trial and error to determine which setting GSAS uses as a
default for I M 3 M) might improve the fit by mis-modelling the preferred orientation
as an origin shift of some sort (e.g., by putting the Vanadium at 0, 1/2, 1/2: the 6b
Wyckoff site).
If International Tables Vol A are consulted, 0,0,0 is the origin, as is consistent with the
GSAS symmetry check out put. The CIF file states the Vanadium site is a 2a site; and
in the International Tables 2a is 0,0,0. If you do a Results, Disagl then bond distances
and angle make sense with the Vanadium on the 2a 0,0,0. The bond distances and
angles do not make sense by putting the Vanadium sites other than the 2a 0,0,0 site.
Following are screen dumps of powder patterns of Vanadium calculated using the userfriendly Powder Cell program (left) and Poudrix program (right) (both are distributed
on the CD-ROM). Both allow you to cross validate the GSAS calculated powder
pattern and Powder Cell also allows you to input the Wyckov position.
58
Thus a conclusion to make of all of this is you have to be very careful with space
groups and Rietveld refinement. You also have to be careful to be on the lookout for
bugs in space group generation code.
Rather than try to model the texture on this trace phase, we will fit the Vanadium
intensity by doing a model biased Le Bail fit which allows all the intensities to freely
float. To fit the Vanadium intensities using a model biased Le Bail fit, go to the LS
Controls tab and select F(calc) Weighted (model Biased) for phase 2 (the
Vanadium).
Run Powpref and Genles and evaluate the result in LivePlot. The intensities now
match quite well.
Under the Phase Tab, Phase 2 ICON, Release the UnitCell for Vanadium and run
Genles. The fit might improve a trivial amount, as the Unit Cell given in the ICSD is
quite accurate for this diffraction pattern. From the point of view of trying to refine the
59
wavelength of silicon, dont spend too much time on the Vanadium. It is unlikely to
significantly affect the determination of the wavelength.
Again, to record the wavelength, Zero and ESDs, open LSTVIEW (ICON 2nd from the
right on the top EXPGUI program bar) and scroll down to the bottom to find the
C/L1/R/2Th (wavelength) and Zero.
60
SECTION 9
Combined Refinement of multiple datasets (X-ray and
Neutron)
Important: Combined X-ray and Neutron refinement can seem quite nifty and
high-tech, but it should be done for a well defined and definite reason. Often, it
can be best to just refine on the neutron powder diffraction data as, in
comparison to X-ray data, it can be less affected by systematic errors. If the
individual X-ray or neutron data is not adequate by themselves, combined
refinement can be beneficial. In practise, the following structure would
normally just be refined using the neutron data.
Important: If the Sum(w*d**2) for the histograms/diffraction patterns are
very unequal, histogram weighting may be required so the datasets are equally
weighted and this is shown in the following tutorial. A rule of thumb can be to
weight the neutron data such that the Sum(w*d**2) for the neutron data is 1.2
times that of the X-ray data. Histogram weighting is enabled via the Expedt
program (via the expedt menu: k p h f). Powpref must be run after setting any
new histogram weighting.
Important: In joint refinements, other Rietveld users would usually not start
with both data sets, but get one looking OK before introducing the additional
data. A suggestion would be to follow this strategy if the following guide does
not work.
Adding multiple diffraction datasets into GSAS is just as easy as adding a single
dataset. Using both X-ray and Neutrons together can be very useful, though some
thought can be required. The datasets should be on an identical sample, run at the
same temperature, and the diffraction data should be seeing consistent properties of the
structure (refer: I.E. Grey, L.M.D. Cranswick and C. Li, Accurate site occupancies for light atoms from
powder X-ray data? Oxygen vacancy ordering in 6H-BaFe0.67Ti0.33O3-delta (delta = 0.08 and 0.32),
Journal of Applied Crystallography, 1998, Vol.31, No.Pt5, pp.692-699). In this example, we are
going to refine the structure of IUCr Rietveld Round Robin PbSO4 using both the
X-ray and neutron data (R. J. Hill, Rietveld refinement round robin. I. Analysis of standard X-ray
and neutron data for PbSO4, J. Appl. Cryst. (1992). 25, 589-610).
on the desktop, and the "Select an experiment
file to read" dialog will be displayed. Browse to: c:\cpdw\lebail_xray_neutron
directory, type in pbso4 and click READ followed, when prompted, by Create to
create a new EXP file. Put in the extra title information as required.
Add a phase and import the structure from the file named
c:\cpdw\lebail_xray_neutron\pbso4_icsd_76925.cif
61
Now add the X-ray dataset by using the Add New Histogram icon in the Histogram
tab. The data file is c:\cpdw\lebail_xray_neutron\pbso4xrd.gsa and the instrument
parameter file is c:\cpdw\lebail_xray_neutron\cuka12xrd.prm . Again, fix up any
problems with the Ratio of the wavelengths (0.5). As POLA is set at a value for a
curved graphite diffracted beam monochromator based on using the Azaroff function
(0.911), IPOLA should be set to 1 to get GSAS to use the Azaroff function. (1).
Now repeat the same procedure to add the neutron dataset by using the Add New
Histogram icon in the Histogram tab. The data file is
c:\cpdw\lebail_xray_neutron\pbso4neu.gsa and the instrument parameter file is
c:\cpdw\lebail_xray_neutron\neu_d1a.prm . The Instrument parameter file has two
banks, select bank one (EXPGUI will not let you proceed until you choose a bank).
If you look in the Histogram tab you will now see one line per histogram (one X-ray
histogram and one neutron histogram). To see the parameters for a particular
histogram, click on that line.
62
(Left: X-ray histogram; Right: neutron histogram)

For the profile fitting, we are going to do this in Model Biased Le Bail mode. Go into
the LS Controls tab. Click on Histogram 1 (X-ray data), and select F(calc)
Weighted.
Now click on Histogram 2 (Neutron data), and select F(calc) Weighted.

Now, prior to fitting the background, run Powpref and Genles
63
Now, select Powder, Bkgedit and fit the background for Histogram 1 (the X-ray data).
If the X-ray histogram is not selected, via the top Bkgedit menu, select File,
Histogram 1.
Now, making sure Histogram 2 (Neutron data) is selected via the L S Controls, select
Powder, Bkgedit and fit the background for the Neutron data. If the X-ray histogram
is not selected, via the top Bkgedit menu, select File, Histogram 2.

Getting the best fit to the multiple diffraction patterns can be more tedious than just
fitting a single diffraction dataset but it is not that difficult. One trick when fitting a
combined X-ray and Neutron dataset is to let the wavelength for the neutron dataset
refine along with the unit cell. Normally the wavelength for the X-ray dataset is more
well determined, so the X-ray wavelength can be used to anchor the unit cell.
64
Fixing the Scale Factors

Via the Scaling tab, turn off the Scale parameter refinement flags for the X-ray and
Neutron data. (These are turned back on after the Le Bail fitting) Now run Powpref
once, the Genles a few times to get calculated intensities into the observed peaks.
Matching up the peak positions

To help the positions of the calculated reflections match up with the observed:
Refine Cell (Phase tab)
Refine both the Zero and Wavelength for the Neutron data (Histogram Tab,
Histogram 2)
Refine the shft parameter for the X-ray data (ProfileTab, Histogram 1)
In Liveplot, to view the Rietveld plot for the 2nd Histogram, select File, Histogram, 2
from the top Liveplot menu. It is possible to open multiple Liveplot screens so you
can simultaneously follow the Rietveld plots of the various histograms.
Refining width and shape parameters

As per the previous sections, slowly release the width and shape parameters for the
X-ray and Neutron data. You may find you need to play with the X-ray parameters as
releasing all the Width and Shape parameters may go into a false minima where the
peaks are too broad at high angle (not helped by a possible goniometer offset problem
at high angle). It may be best to not release any more width and shape parameters at
this point and only try releasing the other width and shape parameters in the final stage
of the structure refinement where the calculated intensities are constrained to the
atomic structure.
65

For both X-ray and Neutron datasets, now refine the background parameters
(Histogram tab).
66
Refining the atomic parameters

For the moment, turn off the refinement flags for all the profile parameters,
wavelength, zero offset and unitcell (but keep the background refinement flags on.
In the LS Controls, for histogram 1 (X-ray) and histogram 2 (neutron), go back into
Rietveld mode; and in Scaling, refine the scale factor for histogram 1 (X-ray) and
histogram 2 (neutron).
67
Now run powpref following be Genles.
If you were only refining X-ray data, you would release the atoms positions and
thermals slowly in reverse order of atomic number. As this is a smallish structure and
the neutron data is also being used, refine all the atomic positions of the atoms. In the
Phase Tab, put your mouse of the atoms and click the right mouse button. This selects
all the atoms. Now select the X refinement flags box.
Now run genles.
68
Most of the above difference plot looks due to thermal parameters needing refinement.
But it does not hurt to run Results, Disang to check that none of the atoms have gone
a-wandering and are in physically unreasonable positions.
If you were only refining X-ray data, you would release the atoms positions and
thermals slowly in reverse order of atomic number. As this is a smallish structure and
the neutron data is also being used, refine all the thermal positions of the atoms. In the
Phase Tab, put your mouse of the atoms and click the right mouse button. This selects
all the atoms. Now select the U refinement flags box.
69
Now run genles.
Now could be a good time to again release the profile parameters, unit cell, neutron
zero, neutron wavelength, and profile parameters for the X-ray and neutron data. Then
run Genles.
Near the final stages of the refinement, visual changes to the Rietveld plot can be quite
trivial. Thus a better guide can be to look at the fit indices and the refined parameters
70
via the Lstview program and Disang as a judge of how well the refinement is now
progressing.
Cycle 179 There were 8918 observations.
Powder data statistics
Fitted
-Bknd
Bank Ndata Sum(w*d**2) wRp
Rp
wRp
Rp
Hstgm 1 PXC
1 6000 24606.
0.1001 0.0785 0.0984 0.0780
Hstgm 2 PNC
1 2918 24061.
0.0561 0.0454 0.0594 0.0487
Powder totals
8918 48667.
0.0694 0.0683 0.0761 0.0713
Average
DWd Integral
0.724
0.956
0.219
0.915
0.474

Fitted
-Bknd
Rp
wRp
Rp
Hstgm 1 PXC
1 6000 24162.
0.0992 0.0778 0.0971 0.0770
Hstgm 2 PNC
1 2918 26884.
0.0593 0.0478 0.0633 0.0516
Powder totals
8918 51046.
0.0711 0.0685 0.0774 0.0712
Average
DWd Integral
0.729
0.956
0.208
0.915
0.455

Fitted
-Bknd
Rp
wRp
Rp
Hstgm 1 PXC
1 6000 23562.
0.0980 0.0767 0.0954 0.0756
Hstgm 2 PNC
1 2918 26541.
0.0589 0.0475 0.0628 0.0513
Powder totals
8918 50102.
0.0704 0.0677 0.0764 0.0701
Average
DWd Integral
0.735
0.956
0.210
0.915
0.457

Fitted
-Bknd
Rp
wRp
Rp
Hstgm 1 PXC
1 6000 23354.
0.0976 0.0763 0.0948 0.0751
Hstgm 2 PNC
1 2918 24885.
0.0571 0.0461 0.0606 0.0496
Powder totals
8918 48238.
0.0691 0.0670 0.0750 0.0693
Average
DWd Integral
0.737
0.956
0.216
0.915
0.468

Fitted
-Bknd
Rp
wRp
Rp
Hstgm 1 PXC
1 6000 23197.
0.0972 0.0760 0.0943 0.0747
Hstgm 2 PNC
1 2918 26280.
0.0586 0.0473 0.0625 0.0510
Powder totals
8918 49476.
0.0700 0.0672 0.0757 0.0694
Average
DWd Integral
0.739
0.956
0.210
0.915
0.458
Refining thermals anisotropically and checking the

structure using Platon and GUI WinORTEP 3
Important: Be very careful when refining thermals anisotropically using
powder diffraction data. Normally this is only possible with good Neutron
data, and even then due care must be shown to make sure the results are
physically reasonable and releasing these parameters is supported by the data.
Besides looking at the shift/ESDs and ESDs in the GSAS LIST file (via Lstview). If
the shift/ESD for a parameter is not very near zero after a good number of cycles, this
can imply that the data will not support the refinement of this parameter (either alone
or in combination with other parameters). Also run the structure through validation in
Platon and visually inspect the structure using either Platon or GUI WinORTEP 3
(WinORTEP 3 can read GSAS files directly)
To refine the atoms anisotropically that are already refining isotropically, select all the
atoms then click on the Xform Atoms icon. Then select the Set Anisotropic icon
which will convert the Isotropic values to Anisotropic values. Select Close to get back
to the main EXPGUI screen.
71
It would not hurt to run Powpref at this point, followed by Genles to continue the
refinement.
Histogram Weighting
While the shift/ESDs look OK (via lstview) for the anisotropic thermal parameters, it
would be good if the refinement was weighted more on the Neutron data than the
X-rays. The Sum(w*d**2) for the X-ray data is double that of the neutron data, so it
is possible that noise or systematic error in the X-ray data is having more of an
influence on some of the thermal parameters than the better high angle intensities of
the neutron data.
72
Based on the above Sum(w*d**2), it would be good to double the weighting of the
neutron data. Via Expedt, type k p h f 2 (2 is the second histogram, which in this case
is the neutron data). Then enter a new histogram weighting factor of 2 (the default is
1). Now keep typing X [RETURN key] until Expedt exits. Powpref must be run
after changing a histogram weighting. The following Genles screen shows the
neutron data (Histgm 2) is now upweighted compared to the X-ray data, which is what
we want.
ORTEP-3 for Windows for Windows can be obtained from

http://www.chem.gla.ac.uk/~louis/software/ortep3/ (is included on the CD-ROM) and
can imported GSAS EXP files. It can be good to graphically inspect the structure to
see if the ORTEPs make sense, as show in the following screen image.
73
Platon (by Ton Spek) can perform visualisation of crystal structures as well as a large
variety of structure validation. At minimum you should do an Addsym check to see if
the structure may have too low a symmetry spacegroup. Addsym analysis should be
considered mandatory for all solved and refined structures. Platon can also check for
intra and inter molecular bonds that are suspiciously short, and suspicious anisotropic
thermals. The UNIX version of Platon is available via
http://www.cryst.chem.uu.nl/platon/ and the Windows version at:
http://www.chem.gla.ac.uk/~louis/software/platon/ . Platon can read Platon, Shelx and
CIF files, and EXPGUI can export Platon SPF files (via the Import/Export, Coord
Export menu). It can often be best to export CIF files for reading into Platon, as
Platon can then use the ESDs as part of the validation analysis.
74
SECTION 10
Importing a structure using a GSAS macro file, and using
occupancy constraints and charge balance restraints
In this example, there will be a brief example of using the GSAS Expedt macro facility
as well as showing the use of constraints for refinement of site occupancies.
The crystal structure is that of Barium Iron Titanate (I.E. Grey, C. Li, L.M.D.
Cranswick, R.S. Roth and T.A. Vanderah, Structure analysis of the 6HBa(Ti,Fe3+,Fe4+)O3-delta solid solution, Journal of Solid State Chemistry, 1998,
Vol.135, No.2, pp.312- 321.)
Hexagonal; Spacegroup = P 63/M M C
Cell
a=b= 5.6915 c= 13.9521 gamma = 120
Following are the starting co-ordinates and occupancies in GSAS macro format. The
text after the ! are comments.
i
i
i
i
i
i
i
i
1
2
3
4
5
6
7
8
Ba+2
Ba+2
Ti+4
Fe+3
Ti+4
Fe+3
O-2
O-2
0.00
0.33333
0.00
0.00
0.33333
0.33333
0.52
0.83
0.00
0.66667
0.00
0.00
0.66667
0.66667
0.04
0.66
0.25
0.09
0.00
0.00
0.84
0.84
0.25
0.08
1
1
0.5
0.5
0.5
0.5
1
1
Ba1
Ba2
Ti1
Fe1
Ti2
Fe2
O1
O2
i
i
i
i
i
i
i
i
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
!Insert
!Insert
!Insert
!Insert
!Insert
!Insert
!Insert
!Insert
atom
atom
atom
atom
atom
atom
atom
atom
1
2
3
4
5
6
7
8

on the desktop, create a new EXP file (directory
and title of c:\cpdw\occ_constraints\titanate.exp) and add the above Cell information
(but dont add any atoms).
Then add the histogram / powder X-ray diffraction data

c:\cpdw\occ_constraints\titanate.gsa and instrument parameter file of
c:\cpdw\occ_constraints\ cuka12xrd.prm. Again, fix up any problems with the
Ratio of the wavelengths (0.5). As POLA is set at a value for a curved graphite
75
should be set to 1 to get GSAS to use the Azaroff function. (1). Set the number of
refinement cycles to 8, etc.
Using Macro Files in GSAS

The idea behind GSAS macro files is that of files that contain the keystrokes of the
commands and parameters you would use if you were inputting the information by
hand. The advantage of using a Macro file is you avoid tedium and possible
typographical errors, especially if you have a large structure.
To enter the above coordinates in the c:\cpdw\occ_constraints\struct.mac , run
Expedt, and enter the atom editing menu by typing k l a.
Then to use a macro file type @r ( this is the use macro" command), and GSAS will
prompt you to enter a macro file, type struct.mac. After running the macro file, type
L to examining the atom list.
Now keep typing X [RETURN key] until Expedt exits.
76
Run powpref, then Genles and then fit the background using Powder, bkgedit.
Then do a F(calc) weighted Le Bail fit to the data, including refining the background.
Note that with the screen images below, the fit to the high angle data should be very
good.
77
Then lock down all the profile refinement parameters as before, except the
background. Note that with the screen images below, the fit to the high angle data
should be very good. Turn GSAS back to Rietveld mode. And refine the scale factor
Constraining the refinement of the shared occupancy

sites.
Before we can refine the titanium iron shared positions, they have to be linked to
refine to move together and have the same thermal factors. (the summed occupancy
values should be made consistent with the known composition of the material,
unless you tare trying to determine the chemistry from the diffraction data itself)
Note that in reality the Iron and Titanium most likely do not move identically or have
the same thermal factors, but this is a constraint that is necessary due to not having
enough information in the diffraction pattern to model the shared atom sites in an
unrestrained manner.
The assumption with the following restraints is that the two metal sites are fully
occupied. To make these types of assumptions on your materials, some crystal
chemical knowledge must be applied and tested against the diffraction data.
Two separate Metal sites which do not have linked

fractional occupancies
In this case, the two separate metal sites will not have their fractional occupancies
linked. This can be used to help use the diffraction data to refine the chemistry.
Though it can be better to have an elemental analysis to constrain the composition in
the refinement. Metal site one contains atoms 3 (Ti1) and 4 (Fe1). Metal site two
contains atoms 5 (Ti2) and 6 (Fe2).
78
Go to the Constraints Tab and select New Constraint. Select atoms 3 and 4, then
XYZU-F from the Variables List and save the constraint. Repeat this procedure for
atoms 5 and 6. This means while X,Y,Z and thermals will be constrained to move
together, adding Fe into the site with take out an equivalent amount of Ti; and visa
versa.
Now slowly refine the atom positions and thermals. And Fractional occupancies for
the shared metal sites. It may not be possible to release thermal parameters and
occupancies at the same time. This is something you may find out the hard way. Be
wary to make sure things charge balance (we will be doing this later). This structure is
more complicated as there may be Fe+4 as well as Fe+3. Also, vacancies in the
oxygen positions may be possible as well. The large thermals for the Oxygens might
be indicating oxygen vacancies, or may be just large thermals. This can be difficult to
determine with confidence from X-ray data alone.
79
Important: It can be beneficial to set the occupancy values in the shared sites
(consistent with the known composition of the material) to different values and
see if they consistently refine to the same value. This is a good check on the
robustness of the refinement, and also if there might be some dangerous false
minima in the refinement you should be aware of.
Setting up charge balance constraints

We will use the cell composition restrains to set up a change balance constraint. It can
be easier doing this as a GSAS macro (c:\cpdw\occ_constraints\chbal.mac). And
this appears below. Even if you dont wish to apply the constraint, it can be a good
way to do an easy check on whether the refinement charge balances.
k
l
s
c
i
1
1
1
1
1
1
1
1
0
0
1
2
3
4
5
6
7
8
!don't make backup file

!least squares setup
!edit soft restraint data
!edit chemical composition restraints
0.1 !insert new constraint, it should sum to zero with 0.1 esd
2
!phase one, atom 1 (Barium),
value of 2
2
!phase one, atom 2 (Barium),
value of 2
4
!phase one, atom 3 (Titanium), value of 4
3
!phase one, atom 4 (Iron),
value of 3
4
!phase one, atom 5 (Titanium), value of 4
3
!phase one, atom 6 (Iron),
value of 3
-2 !phase one, atom 7 (Oxygen),
value of -2
-2 !phase one, atom 8 (Oxygen),
value of -2
!end inputting the charge balance constraint
To insert the constraint within the chbal.mac file, run Expedt, then type @r and when
prompted, chbal.mac. Then type L and keep pressing the [ENTER] key to list the
restraint. This is telling us that there are too many negative charges. In this exercise,
we are going to assume this is due to oxygen vacancy in the oxygens surrounding the
Fe/Ti sites.
80
Now keep typing X [RETURN key] until Expedt exits. In the Histogram Tab, click
on the Set Histogram Use Flags. This shows the chemical composition/charge
balance restraints are being applied. If you only wanted to use the restraint
diagnostically, you could deselect this.
Run Results, Disang. This shows that O1 is bonded to the Bariums but not O2. Given
the model has Barium fully occupied, any oxygen vacancies are more likely to be in
the O2 site.
Thus release the O2 Fractional refinement parameter. The charge balance restraint
should keep the parameters from going beserk. Again, we might be finding out the
hard way if we need to fix the O2 thermal, or constrain it to be equal to the O1 thermal.
81
Just in case, run powpref; then run Genles to refine. The Oxygen occupancy goes to
greater than 1 (physically unreasonable). It looks like we have to increase the
weighting on the charge balance restraint. Run Expedt and go k l s c . After listing the
restraint, type F 100 to increase the restraint weighting from 1 (default) to 100. Type
X [Return] until you exit Expedt.
If you now run Genles, it still wants to keep the Oxygen occupancy around 1. (full
occupancy). Disabling the charge balance restraint and manually setting the Oxygen
O1 occupancy at various values also upsets the refinement and drives the metal
occupancies to unreasonable values. This could imply our model of Oxygen vacancies
in the O2 site is not valid and that we should look for the problem elsewhere. Often
when a restraint is fighting against the diffraction data, it implies the model behind the
restraint has some flaws or mistakes. E.g., it could imply we have Fe+4 in the
structure; and or we have refined the Ti/Fe ratio off the actual composition.
Important: What type of crap tutorial is this where the tutorial restraint does
not work!? we hear you ask? Often the logic and assumptions behind the
adding of restraints (and some constraints) are not correct, but this may not be
obvious at the time the restraint was added. It is helpful to get used to the idea
that initial versions and assumptions of the structure model may not be correct.
Forcing pre-conceived ideas about the model onto uncooperative data is not a
good way to progress. Instead, consider if there are more appropriate models
that may give a better explanation of the fine points of the diffraction data.
Think of restraints as being like having nuclear weapons: just because you have
the technology does not mean it should be used. Careful thought on if/when it
is appropriate to use a restraint should be considered, and whether it might be
better to collect extra or improved data so the restraint does not have to be used.
One thing that could be tried could be to add another Fe atom to each of the Ti/Fe sites
and define this as Fe+4 using the charge balance restraint and see what values of Fe+4
this might give in the two sites. (it is of course just as easy to do this calculation on a
sheet of paper working out how much Fe+4 would have to be present to charge
balance the structure). This of course assumes the composition has been refined
correctly. This may not be a valid assumption. This is where the analyst has to think
about things, and perhaps get a microprobe or other quantitative chemical analysis of
the sample to fully constrain the composition in the refinement.
82
Two separate Metal sites (of different site multiplicities)

having linked fractional occupancies
Important: The following assumed you know the composition of the material,
and that the initial occupancy values have been setup in GSAS such that it
matches the known elemental chemistry of the sample.
Here, we will enter constraints that if any Iron is taken out of the first shared metal site,
it will be put into the second shared site, and visa versa with the Titanium. This is not
as straight forward in this case as it might initially seem, as the two shared sites have
different multiplicities (i.e., different numbers of atom positions within the unit cell)
In the Constraint Tab, delete the old Fractional constraints that were set up in the
previous section.
Then go to the Phase tab and turn off all the atom coordinate refinement parameters.
Also, reset the occupancies of the two shared sites to 0.5, either by typing them
manually, or selecting the atoms, clicking on the Xform Atoms icon.
83
Type 0.5 in the occupancy box and select Set Occupancies. Doing this when you
need to change a number of atoms can be very convenient. It can also make it easy to
set the thermal and occupancy atom parameters are various values to check the
robustness of the refinement.
Do the same with the thermals of ALL the atoms. This can be a good habit to make
sure we dont slowly go down into a false minima based on the previous refinement.
Reset them all to 0.1
To add the new fractional occupancy constraint where atom occupancy taken out of
one metal site into another, the following logic must be considered.
The metal position at 0, 0,0 has a site Mult/multiplicity of 2. (there are two of
these sites in the full unit cell
The metal position at 1/3, 2/3,0.84 has a site Mult/multiplicity of 4. (there are
four of these sites in the full unit cell
84
This means that if you took 0.25 of occupancy from the 4 fold site and put it into
the 2 fold site, you would be taking 0.25x4= 1 atoms worth of scattering power.
But 1 atoms worth of scattering power in the 2 fold site is 0.5. So the act of
taking 0.25 occupancy out of the 4 fold site puts 0.5 occupancy in the 2 fold site.
Thus in the new occupancy constraint, if the multiplier for the 4 fold site is 1,
the multiplier for the 2 fold site is 2.
Now here comes the fun bit. In the Constraints tab, select a new constraint and input
the above information to match the following screen image. The New Column button
allows you to add extra atoms into the new Frac constraint. Note that the 0 0 0 site has
a multiplier of 2 for the Ti1 and 2 for the Fe1.
Select the Save button to apply the constraint.
As you have significantly reset the structure, run powpref and genles, then slowly
release the atom coordinate, thermals (and Fract for the shared occupancy sites), heavy
atoms first, followed by light atoms later. You will notice the occupancies of the two
shared sites sum to 1. Fe taken from Fe1 was put into the Fe2 site and visa versa for
the titanium. The summed values for the total cell starting composition is still retained.
85
(i.e., there were 0.5 *2 + 0.5 *4 = 3 atoms of Fe in the cell before the start of the
refinement. After the refinement, 0.263336*2+0.618332*4=3 atoms of Fe, but in
different statistical distribution between the two sites).
This still does not charge balance. You can use the charge balance restraints
diagnostically in EXPEDT (k l s c [RETURN] [RETURN] [RETURN]) or just to the
arithmetic yourself:
+ve charges = +2*2 (Ba1) + +2*4 (Ba2) + +4*2*0.7367 (Ti1) + +3*2*0.2633 (Fe1)
+ +4*4*0.3817 (Ti2) + +3*4*0.6183 =
+33
-ve charge = -2*6 (O1) + -2*12 (O2) =
-36
Sum =
-3
Though personal experience is that GSAS tends to make less typographical errors than
a human when doing the sums. It can be useful to do both methods of a charge balance
check and make sure they both add up. In this case, as shown by the previous section,
it looks like the charge imbalance is probably a combination of the Fe sites containing
a combination of Fe+3 and Fe+4.
86
SECTION 11
Quantitative Phase Analysis (QPA) example using GSAS
Important: It is very easy to get very inaccurate results form quantitative phase
analysis using powder X-ray diffraction, even if the fit looks very good and
reasonable. Thus validation of results (such as XRF analysis, neutron and other
appropriate methods) is pretty much mandatory. Refer to the two International
Union of Crystallography (IUCr) Commission on Powder Diffraction (CPD)
Quantitative Analysis Round Robins (QARR) (published in the Journal of
Applied Crystallography but also available via the CPD website http://www.iucr.org/iucr-top/iucr/cpd.html )
Outcomes of the International Union of Crystallography Commission on
Powder Diffraction Round Robin on Quantitative Phase Analysis: samples
1a to 1h, I. C. Madsen, N. V. Y. Scarlett, L. M. D. Cranswick and T. Lwin,
J. Appl. Cryst. (2001) 34, 409-426
2, 3, 4, synthetic bauxite, natural granodiorite and pharmaceuticals, N. V.
Y. Scarlett, I. C. Madsen, L. M. D. Cranswick, T. Lwin, E. Groleau, G.
Stephenson, M. Aylmore and N. Agron-Olshina, J. Appl. Cryst. (2002) 35, 383400
In this example, we use IUCr Commission on Powder Diffraction quantitative phase
analysis round robin data containing Corundum (Al2O3), Fluorite (CaF2) and Zincite
(ZnO). The diffraction data has been deliberately concatenated, generally meaning that
refinement of atomic co-ordinates and thermals should not be performed. In this case,
while the unit cell can be refined, you have to obtain reliable atomic coordinate,
thermal and occupancy information. If this is not valid for your sample, it can add
extra systematic errors to the result.
87

and title of c:\cpdw\quant\1g.exp).
Import the three CIF structure files one after the other by using the Add Phase:
c:\cpdw\quant\corundum_icsd_10425.cif (when promped, change
spacegroup from R -3 c H to R -3 c)
c:\cpdw\quant\fluorite_icsd_29008.cif
c:\cpdw\quant\zincite_icsd_26170.cif
This leads to the following EXPGUI screen where each phase can be selected via its
phase number. If there is a Uiso value of zero, this may have reset to a reasonable
value as defined by structures in the ICSD.
Also be wary that B values may have been imported and interpreted as Uiso values.
(you can verify this by looking inside the CIF file with a text editor such as notepad)
These need to be reset to Uiso values. The zincite and fluorite structures have Biso
values inputted as Uiso values and these need to be reset.
Biso = 82Uiso : Uiso = Biso/78.96. So just this formula to convert the Biso to Uiso
values.
88
Now add a diffraction pattern (C:\cpdw\quant\cpd-1g.gsa) where the Instrument

Parameter file is C:\cpdw\quant\cuka12xrd.prm . Again reset any bad instrument
values (Ratio=0.5, IPOLA=1, POLA=0.911) and change the number of LS cycles to 8.
In the Scale tab, disable the global scale factor and enable the Phase Fractions Scale
parameter.
89
Run Powpref and Genles. It might be best to exclude the lower angle region where
you are no peaks, but an increasing background due to air scatter.
If you excluded a region, run Powpref and Genles again. Then fit the background as
before using Powder, Bkgedit.
90
Constraining a single shft parameter to all phases

Important: The sample displacement parameter should be the same for all
phases with the sample, thus we need to constrain this to refine to an identical
value within all the phases. (remembering that this is Bragg-Brentano flat plate
geometry data)
Go into the Constraints tab. Select the Profile tab within.
Select Add Constraint, followed by selecting #10 (shft) and continue.
Then select all the (three) phases via the mouse using click and drag. Then Save to
create the restraint.
91
Now release the refinement parameters for shft and the unit cell for all the major
phases (in this case, all the phases are present in major amounts). Now refine in
Genles.
Now fit the profile. Assuming you are using an appropriate starting profile values
from the instrument parameter file, you may find that you only need to release the GW
and LY to get a good fit on such a short range of data. If there was evidence of
preferred orientation, you would also have to refine preferred orientation parameters
for the affected phases.
92
Now refine the background.

The fitting is pretty much done, so go into lstview to obtain the quantitative phase
analysis results.
Phase/element fractions for phase no.
Hist Elem:
1 1 PXC
Fraction :
6.16743
Sigmas
:
0.356722E-01
Shift/esd:
0.00
Wt. Frac.:
0.33291
Sigmas
:
0.128451E-02
(Corundum)

Hist Elem:
1 1 PXC
Fraction :
12.0252
Sigmas
:
0.474497E-01
Shift/esd:
0.00
Wt. Frac.:
0.33137
Sigmas
:
0.874254E-03
(Fluorite)
Phase/element fractions for phase no. 3 (Zincite)

Hist Elem:
1 1 PXC
Fraction :
23.3777
Sigmas
:
0.697861E-01
Shift/esd:
0.00
Wt. Frac.:
0.33572
Sigmas
:
0.665731E-03
Phase/element fraction sum(shift/error)**2 :
0.00
This compares with the mixed and XRF values (%):
As Mixed
XRF
Corundum
31.37
31.70
Fluorite
34.42
33.86
Zincite
34.21
34.01
93
SECTION 12
Applying a QPA GSAS EXP file to a new diffraction file
reasonable. Thus validation of results (such as XRF analysis, neutron, etc) is
important do implement, especially in the development stages of working on a
new phase system; and as spot checks to ensure nothing untoward has occurred
that is throwing the accuracy out.
At present, replacing histogram files is done via the EXPEDT program (the
comprehensive GSAS EXP file editor by Bob von Dreele and Allen Larson). Select
the EXPEDT ICON from the top left menu.
In EXPGUI, save the current GSAS EXP filename as 1h.exp.
Then to get to the point where you can replace the histogram, type K P H R 1 (note
the descriptors within EXPEDT which explain what these mean while you are doing
this). When prompted with Enter raw histogram input file name (<?>,$,QUIT),
type the name of the data file: cpd-1h.gsa and when prompted, confirm this is correct
by typing Y. When prompted with Enter POWDER instrument parameter file
name (<?>,$,QUIT), type the name of the GSAS instrument parameter file:
cuka12xrd.prm and when prompted, choose scan number 1. Dont bother
previewing it. Then type T (Set max 2-Theta or Energy or min TOF), and then / to
confirm the maximum angle is acceptable. To exist EXPEDT, type X X X and
[RETURN], the X and [RETURN].
Check the EXP file is OK, especially in the Histogram tab as some of the Instrument
parameters may not have been imported correctly. Again, fix up any problems with
the Ratio of the wavelengths (0.5). As POLA is set at a value for a curved graphite
should be set to 1 to get GSAS to use the Azaroff function. (1). Correct these.
94
Now run powpref followed by Genles which, as the patterns are close to each other,
should pretty much complete the refinement.
The fitting is pretty much done, so go into lstview to obtain the quantitative phase
analysis results.
Hist Elem:
1 1 PXC
Fraction :
6.75558
Sigmas
:
0.359036E-01
Shift/esd:
0.00
Wt. Frac.:
0.36393
Sigmas
:
0.123027E-02

Hist Elem:
1 1 PXC
Fraction :
12.3218
Sigmas
:
0.451448E-01
Shift/esd:
0.00
Wt. Frac.:
0.33887
Sigmas
:
0.820825E-03

Hist Elem:
1 1 PXC
Fraction :
20.7362
Sigmas
:
0.625926E-01
Shift/esd:
0.00
Wt. Frac.:
0.29720
Sigmas
:
0.630482E-03
This compares with the mixed and XRF values (%):
As Mixed
XRF
Corundum
35.12
35.35
Fluorite
34.69
34.26
Zincite
30.19
30.03
95
SECTION 13
Quantitative phase analysis involving preferred
orientation
reasonable. Thus validation of results (such as XRF analysis, neutron and other
appropriate methods) is pretty much mandatory. Refer to the two International
Union of Crystallography (IUCr) Commission on Powder Diffraction (CPD)
Quantitative Analysis Round Robins (QARR) (published in the Journal of
Applied Crystallography but also available via the CPD website http://www.iucr.org/iucr-top/iucr/cpd.html )
1a to 1h, I. C. Madsen, N. V. Y. Scarlett, L. M. D. Cranswick and T. Lwin,
J. Appl. Cryst. (2001) 34, 409-426
2, 3, 4, synthetic bauxite, natural granodiorite and pharmaceuticals, N. V.
Y. Scarlett, I. C. Madsen, L. M. D. Cranswick, T. Lwin, E. Groleau, G.
Stephenson, M. Aylmore and N. Agron-Olshina, J. Appl. Cryst. (2002) 35, 383400
In this example, we use neutron powder data collected on a corundum crucible
containing cubic Y2O3. The aim here was to check that the corundum crucible being
used for a specialised insitu neutron diffraction experiment would also work as an
internal standard to follow the formation of crystalline and amorphous material.
Corundum Crucible :
Y2O3 :
2.211g 83.0 %
0.453g 17.0 %

and title of c:\cpdw\preferred_orientation\crucible.exp) .
Import the two CIF structure files one after the other by using the Add Phase:
c:\cpdw\preferred_orientation\corundum_icsd_10425.cif (when promped,
change spacegroup from R -3 c H to R -3 c) Change the UISO values from 0
to 0.01.
c:\cpdw\quant\y2o3_icsd_26190.cif (ignore the EXGUI warning that I a 3 is
likely incorrect) Change the UISO values from 0 to 0.01.
This leads to the following EXPGUI screen where each phase can be selected via its
phase number. If there is a Uiso value of zero, this may have reset to a reasonable
value as defined by structures in the ICSD (for inorganics, often a starting UISO
value of 0.01 is used. As this is neutron powder diffraction data, thermals/UISO can
be refined in cases which would not be possible with X-ray powder diffraction data.
96
Also be wary that B values may have been imported and interpreted as Uiso values.
(you can verify this by looking inside the CIF file with a text editor such as notepad) If
Bisos are present, they need to be reset to Uiso values using the formula: Biso =
82Uiso : Uiso = Biso/78.96.
Now add a diffraction pattern (C:\cpdw\quant\cructs.gsa) where the Instrument
Parameter file is C:\cpdw\quant\c2_1_3A.prm . Reset any bad instrument values.
Though in this example, the instrument parameter has no false information within it.
In the Scale tab, disable the global scale factor and enable the Phase Fractions Scale
parameter.
97
In LS Controls, set the number of cycles to 9. Run Powpref and Genles and check
the initial fit with Live Plot. You can specify that phase names be displayed in the
legend by Options, Configure Tickmarks, Label by Name.
Even though the background looks very simple, out of habit, fit the background as
before using Powder, Bkgedit.
98
As this is capillary neutron data, it is usual to refine the Zero offset (not the sample
displacement as this only makes sense for Flat Plate diffractometer data). Refine the
Zero Offset and the Unit Cell for the two phases.
Now fit the profile and refine the atomic positions and thermals/UISOs. This would
not normally be possible so easily with X-ray powder diffraction data.. Assuming you
are using an appropriate starting profile values from the instrument parameter file, you
may find that you only need to release the GW and LY to get a good fit on such a short
range of data. As this is neutron data, the heavy atoms and light atoms have similar
scattering factors and the atomic can be released at the same time. Also refine the
background.
99
You will see from the above screen image that some reflections are not fitting well
with the corundum. Be careful that this could mean we have incorrect structural
information, the refined parameters are in a strange false minima, or the data is flawed,
or suffering preferred orientation. (For some people, if the data has preferred
orientation, this means the data is flawed and you should try a type of sample
preparation and data collection that eliminates the preferred orientation: e.g., spray
drying sample preparation of the powder). All this should be checked.
Zoom up in LivePlot and do CONTROL left mouse click near the HKL lines of the
affected . This will display the affected HKLs.
While a number of HKLs can be investigated, it looks like preferred orientation

involving the 006 direction. In this example, we will use the March-Dollase correction
options within GSAS. Go into the MD Pref Orient tab and put 0 0 6 for corundum
(Phase 1) and set ratio to refine.
100
Before refining the preferred orientation, run LSTVIEW and check the state of the
quantitative analysis.
Corundum:
Y2O3:
81.9% (0.2)
18.0% (0.5)
Now run Powpref and Genles. This seems to fix up most of the mis-fitting of the
data.
Everything that looks reasonable to do has been done. Run LSTVIEW and check the
result of the quantitative analysis.
Corundum:
Y2O3:
81.8% (0.1)
18.1% (0.4)
This compared with the weighed values:

Corundum Crucible :
Y2O3 :
2.211g 83.0 %
0.453g 17.0 %
It seems that the preferred orientation correction does not affect the quantitative
analysis significant, which is nice. It can be good to keep track of how the quantitative
analysis results change as a function of the parameters that are being varied. If some
parameters cause the result of interest (in this case quantitative phase analysis) to vary
quite considerably, then extra effort should be put into seeing if the parameters are
going to reasonable values. With X-ray data, often refining thermal parameters with
inadequate data can cause the quantitative analysis to become very inaccurate. In that
case, trying to fix the values based on literature values can be a decent thing to try.
Cross validating the results with XRF/Chemical analysis can also be very useful to
ensure the results are physically reasonable.
101
Appendix 1: Additions/corrections
April 2007: Lachlan Cranswick: Check tutorial prior to workshop
July 2005: Lachlan Cranswick: Replace first X-ray example with
an easier neutron example. Add page numbers to index. Add a
section on refining the wavelength on neutron data including
problems with spacegroup settings. Add section on quantitative
phase analysis involving preferred orientation.
15 April 2005: Lachlan Cranswick: Misc updates for the TroisRivires, Qubec Workshop on Powder Diffraction and Rietveld
Analysis Thursday 12th May to Friday 13th May 2005.
14 June 2004: Lachlan Cranswick: Misc typographical corrections.
Directory depth not in Section 1. Corrections to refinement strategy
in Section 2, and clarifying on the Azaroff function for diffracted
beam monochromators (when IPOLA=1) in other sections.
01 April 2004: Lachlan Cranswick: Misc typographical corrections.
102

GSAS Rietveld and EPXGUI Software Practicals

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GSAS Rietveld and EPXGUI software practicals

Installing GSAS, EXPGUI and example files

An Easy start: refining the structure of corundum powder using

Creating a GSAS neutron instrument

Refining a standard for a dual wavelength X-ray diffractometer

03a: P. 31 to 32 Creating a GSAS XRD instrument parameter file using INSTEDIT

Applying an existing GSAS EXP file to a new diffraction data file

(File can be freely used and redistributed for

Importing a Cif structure file and determining

Model based Le Bail fitting using GSAS for

True (model-less) Le Bail fitting using GSAS

Problems with space group settings and determining the

Combined Refinement of multiple datasets (X-ray and Neutron)

Importing a structure using a GSAS macro file, and

Quantitative Phase Analysis example using GSAS

Applying a QPA GSAS EXP file to a new diffraction file

Quantitative phase analysis involving preferred orientation

Installing GSAS, EXPGUI

To update GSAS to the latest version, download the GSAS distribution

To update to the latest version of EXPGUI, download the latest

Adding a Crystal Structure manually into GSAS

Creating a generic GSAS Instrument Parameter file

Adding a Histogram (diffraction data) into GSAS

Fitting the background using BKGEDIT

Getting the best fit to the peak profile

Important: There is no fixed method of performing a Rietveld refinement in

Refining the background

Refining the atom positions

The refinement is pretty much over.

Examining the Rietveld plot

Checking the structure

Adding a Crystal Structure manually into GSAS

CeO2 is a Cubic structure with the following crystallographic details:

Creating a starting GSAS Instrument Parameter file

Adding a Histogram (diffraction data) into GSAS

Fitting the background using BKGEDIT

Getting the best fit to the peak profile

Important: There is no fixed method of performing a Rietveld refinement in

Refining the background

Refining the atom positions and thermals

Examining the Rietveld plot

The very high angle peaks also seem OK.

Checking the structure

Replacing a powder histogram (diffraction data file)

taken on an older diffractometer (though pretty much identical in setup and

Risks of releasing too many parameters

Releasing the trns (sample transparency)

Old B-B Diffractometer (left) vs new B-B diffractometer (right)

Not releasing the trns (sample transparency)

Old B-B Diffractometer (left) vs new B-B diffractometer (right)

Spurious peaks: in this case Cuk and Tungsten

Then select and import the y2o3_icsd_26190.cif file in the c:\cpdw\y2o3_pola

Change I a 3 to I a 3. Under more complicated circumstances, the space group and

Select Add Atoms to finish importing the structure into GSAS.

where due care is required as parameters may be unexpected correlated. In the LS

Now add in the diffraction data/histogram. c:\cpdw\lebail_model\canbo-v.gsa is the

Fixing the Scale Factors

Wavelength = 0.692 Angstrom; Polarisation of the X-ray beam (IPOLA=0) of

Double click the EXPGUI icon

(Left: first run of genles; Right: second run of genles)

(with peak concatenation with peak cut-off at 0.001)

(setting the peak cut-off at 0.0001)

Then select and import the si_icsd_51688.cif file in the c:\cpdw\silicon_neutron