Steps in Refinement

This section is taken largely from Cranswick and Swainson [7].

Additional information is given there, with many figures showing the
interface window and many specific examples. The program offers
many options, but the instructions here are limited to those you are
expected to use in these tasks.

1. Run EXPGUI. This opens a text window and an interface

window. Use the interface window to set refinement
parameters. Some results will be returned to you in the text
window, which can also be used to monitor the .lst file. The
interface window has drop-down menus at the top that lead to
usa-buttons that call for specific action and tabs that take you
from one window to another. From here on, instructions are
given only for this window (in terms of menu, usa-button, or
tab).
2. Open a new or existing .exp file. When you first run EXPGUI,
the program instructs you to open an existing file.
If EXPGUI is already running, you may open a file using the
file drop-down menu. If you wish to create a new file, type in
the desired name and click the read usa-button.
3. Enter crystal structure data for phases in the .exp file. Note
that qualitative analysis must be done (JADE is one of a
number of graphical display programs for XRD data) before
undertaking the refinement. (Note that the GSAS program
refines rhombohedral structures in the hexagonal setting.) To
enter structure data, select the phase tab and then the add
phase usa-button. This will bring up an add new phase dialog
where you input the phase title, the Space Group (R –3 c)
(make sure to include the spaces), and the unit cell values.
Then select the add usa-button. GSAS will then give a
symmetry analysis output for you to check to make sure you
have entered the space group correctly (use the International
Tables or similar database to validate the output).
Select continue once you are satisfied with the structure
data. This will give the main EXPGUI screen with the cell
information but no atoms.

Now select the add new atoms usa-button and add in the atom
information using the keyboard.
 Select the add atoms usa-button to go back to the
main EXPGUI screen where all the crystallographic
information is now visible. The GSAS default values for
vibrational parameters, UISO (0.025), are usually too large for
inorganic structures, so it is better to reset the starting UISO
values to 0.01 (by selecting the UISO values one at a time with
the mouse and changing to 0.01). The structure database
contains vibrational parameters, which are generally best
retained and not refined.

An alternate way to add phase data is to import it directly from

the database. This approach can be used after you gain
experience entering the structure data manually. When you
select the add phase usa-button and a new box appears, use
the option in the lower right to import the phase data. Four
options for import file format are provided--select
the GSAS .exp format (the .cif format is also provided in the
database), which will open a third box to search
subdirectories for the appropriate .exp file for the phase you
wish to load. After selecting a specific .exp file, the add new
phase box will be automatically filled out with the data for
that phase. If the .exp file contains multiple phases, a list will
be shown for selection of the specific phase.
Select Continue and a list of symmetry operators appears;
upon acceptance of the defaults, a list of atoms, coordinates,
occupancies and vibrational parameters is displayed.
Select add atoms to complete the import of the remaining
structure data as a new phase. You may wish to replace the
default phase title in EXPGUI to the actual phase name,
otherwise it reflects the path and filename of the .exp file.
4. Create or open an instrument parameter file. For the tasks in
these instructions, open the file provided, which contains the
parameters from Stutzman for the powder data used here. But
if you wish to create a new file, select from the top
menu Powder, Instedit.

The instrument parameter file format is discussed in

the GSAS manual (page 228).

5. Open a histogram (powder diffraction data). Select

the powder tab followed by the add histogram usa-button.
Find and add the data file and the instrument parameter file. If
you wish to edit this file, select from the top menu Powder,
Instedit.
6. Fit the background. This is a preliminary fit, which you will
refine below. First run powpref followed by genles using the
usa-buttons. Then fit a GSAS background function to the
data. 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 load new.
7. Fit the profile. In the profile tab, set the profile
type to 3 (Pseudo-Voight with Finger-Cox-Jephcoat peak
asymmetry function).
8. Perform refinements. For each refinement, run genles using
the usa-buttons, preceeded by powpref when you have
changed specific variables such as peak profile cutoff, or peak
profile, sample displacement, or an instrument
parameter. GSAS generally will warn you if you are
attempting to run genles after changing a key parameter.
Run liveplot (and keep this window open) to see the state of
the refinement in terms of how well the calculated pattern is
fitting the data. 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 to match
the observed pattern so the difference is as close to a flat line
as possible. Set the number of cycles to 8 and in
the profile tab set the profile cutoff to 0.001. (Since you
have changed the peak profile cutoff, you will need to
run powpref before you run genles.)

There is no fixed order in which to release parameters when

performing a Rietveld refinement. Ideally, all parameters
should be refined simultaneously. But when refining
complicated mixtures like clinker or cement, some phases and
parameters inevitably correlate, and a sequential refinement
reduces the likelihood of problems related to the correlations.
The instructions here provide suggestions and should not be
blindly followed in all cases.

Monitor the difference profile plot to assess your refinement. A

valid refinement shows only minor differences between
computed and measured patterns.

Monitor the Χ2 in the text window. If this increases

progressively, the refinement is diverging and you should stop,
determine which highly-correlated variables may be creating
the divergence and deselect refinement of one, or revert to an
earlier .exp file (see the section titled Helpful Hints) and then
continue. A correlation matrix is included in the .lst file if Print
Option #2 of the LS Controls tab of EXPGUI is selected..

Multiple parameters may be refined at the same time, but you

must be careful if the parameters are cross-correlated, as
refinement results may be misleading. The correlation matrix
indicates parameters that are cross-correlated. For some
parameters a constraint makes sense and reduces potential
correlations. For example, specimen displacement affects all
phases similarly so a constraint in the peak profile parameters
for this variable will hold each to the same value (set through
the Peak Profile Constraints window).

Refine scale and background.

Refine the shift, unit cell parameters, and peak (GV) width.

Set peak profile cutoff to 0.001 and run powpref and then
genles.