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PowderCell : a mixture between crystal structure visualizer, simulation and

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 PowderCell : a mixture between crystal structure
visualizer, simulation and refinement tool
Gert Nolze *
Federal Institute for Materials Research and Testing, 12205 Berlin, Unter den Eichen 87, Germany. Corre-
spondence e-mail: gert.nolze@bam.de

The program PowderCell is a crystallographic tool for visualization of crystal

structures. However, it offers also non-conventional features like the fulautomati-
cal generation of subgroups or the consideration of non-standard settings of space-
group types. On the one hand the program is very useful for non-crystallographers
who like to get an impression of the atomic arrangement within the unit cell. But
also for crystallographers it is recommendable because it contains a lot of addi-
tional information which can be extracted and used like data given in the Interna-
tional Tables for Crystallography, Vol. A. However, the most important advantage
of the program is the simultaneous calculation of the X-ray or neutron diffraction
powder patterns for a mixture of up to 10 crystalline phases. Between more than 7
different characteristic radiations can be chosen and their influence on the result-
ing powder pattern can be studied. Furthermore, experimental diffractograms can
be analysed using a refinement procedure. The implemented LeBail-algorithm al-
lows the investigation of unknown phases. In combination with the refinement
algorithm an interface to Shelx offers the possibility for a step by step ab initio
structure analysis. Certainly, the user-friendly shell is one reason that especially
users who are not so familar with space-group symmetry, crystal structure data
or diffractometry use this powerful tool for the solution of scientific or analytical
c 0000 International Union of Crystallography
problems as well as in teaching.

1. Introduction Wendschuh-Josties (calculation of anomalous scattering factors

Nearly ten years ago, in the summer of 1992, the project Pow-
derCell has been started. The reason was that in those days the
structure refinement from powder data was very uncomfortable
for beginners. On the screen only a lot of running numbers and
remarks were visible and after some hours a refinement pro-
cedure was finished without any tool to vizualize the resulting
crystal structure suggestion or to show the difference between
experimental and refined powder pattern. So the idea was born
to create a crystallographic tool for a user-friendly visualization
and manipulation of crystal structures combined with the calcu-
lation of diffraction pattern. Very often discussions showed that
crystallographers specialized on the solution of crystal struc-
tures had certain imaginations about possible structure models.
They were looking for a tool to simulate a structure model by
translation and rotation of molecules within the unit cell and
study the generated variation of the powder pattern.
Additionally, on Residual Stress meetings non-
crystallographers demonstrated their own developments of pro-
grams for the simulation of a diffractogram, mostly for special
assumptions (e.g. only for cubic materials or metals, no con-
volution of the line intensities, no general export filters etc.).
However, not only the quality of the software but also the fact
that they spent a lot of time for a tool which actually should
be available for any scientist, engineer and technician whithout
any fee was one impulse for the development of PowderCell
by W. Kraus and G. Nolze. Sometimes the solution of spe-
cial problems were supported by an active assistent, e.g. by M.
for different radiations), U. Müller (elaboration of subgroup re-
lations), G. Reck (interaction of single crystal structure analysis
and powder data) and B. Müller (size and strain).
Once the aim of the program was the generation of structure
models by a manual movement or the investigation of the influ-
ence of the crystal structure using the comparison of experimen-
tal data and the calculated powder diffraction pattern (Kraus &
Nolze, 1996). In these days the automatical refinement proce-
dure substitutes the manual mode as far as possible. But it is
not a typical black box system like other powderful programs
in former time. It is rather so that the influence of a lot of pa-
rameter which existed also in older and powerful software has
been vizualized so that the user gets a feeling about that what
he is doing. Thus the aim of PowderCell has been adapted step
by step on the requirements of current problems of the authors
or users who are distributed worldwide.
2. Requirements and limitations
On the one hand a program should be based on a sure code
for generation of crystal structures and calculation of the re-
sulting powder patterns, on the other hand it should be possi-
ble to control it very easyly by the user. Therefore it was one
of the first intensions to create a format for crystal structure
data which contains the only necessary input data: lattice pa-
rameters, atomic coordinates, atomic number for the definition
of the atomic scattering factor, substitution and occupation and
the temperature factor. One example is given in Tab.1 which is
based on data of ICSD (Inorganic Crystal Structure Data base,
Karlsruhe, Germany). Especially older programs like LAZY 36.9% of all sites are occupied by Si. In sum only 86.9% of
PULVERIX (Yvon et al., 1977) requires a formatted data in- all generated symmetry-equivalent positions (4 in the unit cell)
put what is usually time consuming to generate. The data listed are occupied statistically. The substitution of Al by Si can be
in Tab.1 seems to be formatted but this is not required. Only derived by the ratio of 36.9/86.9 ≈ 0.425, what means that
some conditions should be noticed which are contained in the 42.5% of Si substitutes the Al, if we would assume, that only
following list of general remarks to the data file format used: 86.9% of all places would be occupied by Al. For the third Al-
coordinate a probability of 13.1% exist, that this site is occupied
• The first line contains the keyword CELL followed by by an Al-atom.
the lattice parameters ao , bo , co , α, β and γ. All numbers
must be given and have to seperate at least by one blank.
• Each atomic position of the asymmetric unit must be de-
scribed by a label, e.g. by the atomic symbol as in Tab.1,
the atomic number and the atomic coordinates. All data
have to be seperated by at least one blank. For the label
the first 4 letters will be used. Instead of the atomic num-
ber the ionic state can be written, e.g. for 13 it is allowed
to write Al or Al3+. Optionally a site occupation factor
(SOF) multiplied by a substitution can be added as well
as the isotropic temperature factor Biso . In case of the use
of Biso the input of the SOF is required, like shown for
the first Al-atom. Please notice that only Biso has to be
entered and not u or β or the corresponding anisotropic
values.
• In the last line the space-group symmetry must be defined
followed by the used setting. If the setting number is 1 it Figure 1
Used structure data editor in PowderCell . Beside the entered lattice parameter
can be omitted. For the space-group type the space-group and atomic coordinates, the cell volume, the X-ray density and the relative mass
number of the International Tables for Crystallography of the unit cell will be calculated and given.
(Hahn, 1995) has to be used. For space-group number 55
(P bam) of our example in Tab.1 three different settings The Windows version of PowderCell offers a special data
will be considered by PowderCell : P bam (setting 1 and file editor in which the initial structure data file can be created
2), P mcb (setting 3 and 4) and P cma (setting 5 and 6). within the program. There in a mask all data have to be entered
starting with the space-group number and the setting. This has
Table 1 the advantage, that on one hand the Hermann-Mauguin symbol
The examplary set of crystal data for synthetic mullite — Al4.52 Si1.48 O9.74 , will be shown and input errors will be reduced, on the other
(ICSD 66451) — used in PowderCell . hand all other data will be adapted in dependence of the defined
symmetry. So it is only necessary to input the lattice parameter
CELL 7.5460 7.6940 2.8830 90.000 90.000 90.000 ao if a cubic symmetry has been chosen. All other lattice pa-
Al 13 0.0000 0.0000 0.0000 1.0000 1.6100 rameters will be inserted automatically an cannot be changed.
Al 13 0.1487 0.3411 0.5000 0.5000 1.6100
14 0.3690 1.6100
Furthermore, because of the selected space-group symmetry all
Al 13 0.2604 0.2073 0.5000 0.1310 1.6100 conditions for the Wyckhoff positions are available and will be
O 8 0.3575 0.4227 0.5000 1.0000 1.6100 used by the program. For special positions it is possible to en-
O 8 0.1273 0.2206 0.0000 1.0000 1.6100 ter the Wyckoff letter in the corresponding column and only the
O 8 0.0000 0.5000 0.5000 0.6070 1.6100 free degree has to be introduced. This means, that for a posi-
O 8 0.4418 0.0522 0.5000 0.1310 1.6100
RGNR 55 tion {x, y, z} = {0, 1/2, 1/4} no additional input is necessary
whereas for {x, y, z} = {0, 1/2, z} only for z a number must be
introduced.
In Tab.1 it is also demonstrated, how a substitution and/or The best way is the use of existing structure files. Since Pow-
occupation can be considered. For the first Al-atom the value derCell uses an own data file format which can be written very
1 is given. This means that 100% of all generated atomic posi- easy by an ASCII editor these ∗.cel-files can be loaded. How-
tions are occupied and no substitution exists. The next Al-atom ever, for crystals with lower symmetry the number of atoms
is described by a SOF=0.5. This means that only 50% of all in the asymmetric unit increases and it is really uncomfort-
generated positions are occupied by Al. The next line doesn’t able to input all necessary data manually. Therefore an im-
contain any information about the atomic coordinates. There- port of structure files has been implemented reading structure
fore the coordinates of the former line are valid also for this data exported by the ICSD (∗.txt) or generated for the use in
atom (or ion) and it means a substitution of Al by Si because Shelx (∗.res, ∗.ins). But also the use of Crystal Informa-
the atomic number is given as 14. As visible from the SOF only tion Files (∗.cif) is possible.
Table 2 3. Structure representation
Example of an ICSD file (pyrite.txt) which can be imported in Pow-
derCell . The anisotropic temperature factors βi j will be converted into the
isotropic Biso shown in the last column of the structure file editor as B[temp] 3.1. Generation of crystal structure
(see Fig.1).
How does PowderCell generate the crystal structure? For
COL ICSD Collection Code 316 this complex procedure the program uses a data entry in
DATE Recorded Jan 1, 1980; updated Jan 19, 1999
NAME Iron persulfide pcwspgr.dat (Nolze, 1997). This is the symmetry file where
MINR Pyrite - from kyanite mine near York, S. Carolina all information for the different settings are encoded. It is based
FORM Fe S2
= Fe S2 on the symmetry file of RIETAN (Izumi, 1987) but has been ex-
TITL Investigation of the bonding mechanism in pyrite tended by non-standard settings and the information of Wyck-
using the moessbauer effect and X-ray crystallogr.
REF Acta Crystallographica A (39,1983-) hoff positions. Furthermore, generators substitute the origi-
ACACE 32 (1976) 529-537 nally used general positions. For the given examples — Mul-
AUT Finklea, S., Cathey, L., Amma, E.
CELL a=5.428 b=5.428 c=5.428 α=90.0 β=90.0 γ=90.0 lite and Pyrite — Tab.3 and Tab.4 show the symmetry entries in
V=159.9 D=5.02 Z=4 pcwspgr.dat, respectively.
SGR P a -3 (205) - cubic
CLAS m-3 (Hermann-Mauguin) - Th (Schoenflies)
PRS cP12 Table 3
ANX AX2
PARM Atom No OxStat Wyck ---X--- ---Y--- ---Z--- -SOF-
Entry for space-group type P bam (e.g. Mullite) in pcwspgr.dat containing
Fe 1 2.000 4a 0. 0. 0. all symmetry information used in PowderCell .
S 1 -1.000 8c 0.38504 0.38504 0.38504
WYCK c a
TF Atom β(1,1) β(2,2) β(3,3) β(1,2) β(1,3) β(2,3) spgr 55 1 5 1 4 8 2 P b a m
Fe 1 0.0021 0.0021 0.0021 0.0000 0.0000 0.0000 0 2 2 1 1 0 0 0 0 0 0 0 0 0
S 1 0.0025 0.0025 0.0025 0.0000 0.0000 0.0000
REM M PDF 6-710
1 4 3 4 12 4 14 4 100 12 102 12 214 6 216 6
REM M Displacement factors measured for 90, 300, 600 K 4 0 0 0
REM M For moessbauer meas. great cr. from Ambasaguas 3 0.5 0.5 0
RVAL 0.036

Sometimes the crystal structure data will be given in differ-

ent settings described by the same Hermann-Mauguin symbol Table 4
but for shifted origins (Kraus & Nolze, 1998). Therefore an ad- Entry for space-group type P 21 /a 3̄ (e.g. Pyrite) in pcwspgr.dat containing
all symmetry information.
ditional translation vector t can be considered which will be
combined with all atomic coordinates of the asymmetric unit
spgr 205 1 14 1 12 3 3 P 21 /a − 3
(see Fig1). So it is possible to import or enter crystal struc- 3 2 2 1 3 1 0 0 0 0 0 0 0 0
ture data and shift this using t. This procedure enables e.g. the 1 6 61 6 183 22
conversion of the two settings of several cubic and tetragonal 4 0.5 0 0.5
space-group types where the origin of the unit cell is shifted1 . 3 0 0.5 0.5
The correspondence can be demonstrated very easyly e.g. for 13 0 0 0
Silicon. The crystal structure can be described by the position
(1/8, 1/8, 1/8) using the second setting of space-group type
227. However, if one change the setting to the first and use Using the given numbers the Laue group, the existence of
t = (−0.125, −0.125, −0.125) the same structure results ob- inversion centre in the cell origin (first line), the reflection con-
viously because the identical powder diffraction pattern will be ditions (second line), the general and special positions (third
generated. line) and the generators (all other lines; in maximum 5) are
Very interesting is the import of Shelx (Sheldrick, 1990) fixed. More data are not necessary for the description of a space-
files because commonly neither the Hermann-Mauguin symbol group type in PowderCell . Therefore the size of the ASCII-file
nor the space-group number are given. Therefore PowderCell pcwspgr.dat containing the different 740 settings is com-
interpretes the used general positions and tries to convert this paratively small: 120 kByte.
into one of the supported 740 settings of space-group types. For an examplary generation the data of Mullite (Tab.3) shall
Mainly the multiplicities of point groups are used to reduce the be used. There 3 generators are given: type 4 (rotation axis 2z )
number of possible candidates. If in principle no agreement will including a translation vector [0,0,0], type 3 (rotation axis 2y )
be found, because in the data bases sometimes also settings ex- including [0.5, 0.5, 0] and an inversion center (1̄) at (0,0,0). The
ist which are not considered in PowderCell , the program never- generator types are given by the following symmetry matrices:
theless imports all coordinates and sets the space group on P 1;      
after which the user can select the correct space group from the 1̄ 0 0 1̄ 0 0 1̄ 0 0
menue. It may be possible that only an additional translation 2z =  0 1̄ 0  , 2y =  0 1 0  , 1̄ =  0 1̄ 0
vector t must be considered to get the accurate crystal structure 0 0 1 0 0 1̄ 0 0 1̄
description. (1)
1 However, this is not necessary because these two settings are described in PowderCell as well as in International Tables for Crystallography.
 Let us start with a general position (x, y, z). After multipli-
cation with 2z the position (x̄, ȳ, z) has been created. Because
no additional translation must be considered this is the sec-
ond position. Now the two existing atomic coordinates have
to combine with the 2y . However, here we have to consider
an additional translation [1/2,1/2,0]. From (x, y, z) we gener-
ate (x̄ + 1/2, y + 1/2, z̄) whereas from (x̄, ȳ, z) the position
(x + 1/2, ȳ, z̄ + 1/2) results. If now the inversion center will
be considered all general positions are generated:
(x, y, z)
(x̄, ȳ, z)
(x̄ + 1/2, y + 1/2, z̄)
(x + 1/2, ȳ, z̄ + 1/2)
(x̄, ȳ, z̄)
(x, y, z̄)
(x + 1/2, ȳ + 1/2, z)
(x̄ + 1/2, y, z + 1/2)
The number of resulting positions is in agreement with the
multiplicity of the point group mmm, what can be used as one
condition of plausibility.
a) b)
Figure 2
Crystal structure of low-temperature Quartz. a) shows the asymmetric unit and
b) the generated crystal structure by PowderCell .
The generation is running always by this procedure, i.e. all
symmetry matrices will be generated after loading of the crystal
structure file. For low-temperature Quartz the generated crystal
structure is shown in Fig.2. On the left side the content of the
asymmetric unit within the unit cell is given whereas on the
right side the crystal structure is represented. As well known,
the unit cell contains only 9 atoms, but then no SiO4 -tetrahedron
is visible because no tetrahedron is completely included. There-
fore PowderCell allows to increase the volume in which the
crystal structure will be generated. Fig.2b) shows 4 joined tetra-
hedra.
Very often it is wished to know more about the distances and
angles between atoms. This has been enabled by two different
ways. On the one hand it is possible to measure distances and
bond or torsion angles manually by selection of the atoms, re-
spectively. On the other hand a table is generated by the pro-
gram which contains all coordinates of generated positions, the
bond angles, but also general information about the space-group
type used. There the Laue group and point symmetry group are
given, as well as the general and special positions and the type
of the generators used. Fig.3 shows, that beside these also a
sheet subgroups exist, which can be selected.
3.2. Subgroup generation
The use of subgroups may be very sensible if phase transi-
tions will be investigated and no crystal structure data exist.
Subgroups describe a decreasing of symmetry density, i.e. either
the symmetry decreases by a c̈onstantünit cell volume or the
symmetry is conserved but the volume is twice or more higher.
A more detailed and exact description is given in (Hahn, 1995)
or (Müller, 1994), who investigated the Wyckhoff splitting in
dependence of the subgroup relation.
Figure 3
Crystal structure of low-temperature Quartz. a) shows the asymmetric unit uad
b) the generated crystal structure by PowderCell .
Using subgroup relations the symmetry can be decreased step
by step. Until now the benefit of subgroups is well known but
the use of the information given in International Tables for Crys-
tallography is comparativly difficult for an unexperienced user.
To generate the new unit cell and especially the new asymmetric
unit is really complicate. PowderCell is able to do this automat-
ically. The user must only select one of the offered maximal
subgroups and the program adapts the dimension of unit cell
as well as the atomic coordinates. At the end it Unfortunately,
the generation of so-called complete trees of subgroup relations
is impossible. So sometimes no maximal s but any subgroup
can be used. To keep the overview of the numerous possibilities
seems to be then very difficult. One example is the Perovskite,
where the modifications can be explained by the use of sub-
groups.
P m3m
P 4/m mm
P 4mm
C mmm
P bnm
Figure 4
Some subgroup relations for Perovskites which has been observed.
 For Perovskite a lot of different modifications exist. The typ- 3.3. Structure manipulation
ical is the cubic but there are also tetragonal, orthorhombic and In PowderCell exist a lot of tools to manipulate the crystal
monocline modifications. Some exclusiv are shown in Fig.4. structure or parts of it. This include e.g.
There is also shown, on which way the symmetry decreases.
But what does it mean or what is the sense of this behaviour? In • rotation and translation of the generated structure
all cases the crystal structure loses symmetry or gains a degree • generation of more than one unit cell
of freedom. This influences neither the atomic positions or the
lattice constants or both simultaneously. • projection of lattice planes
This is demonstrated in Tab.5, where the Wyckoff-splitting • stereo looking by 6◦ -tilted single pictures
is given for the Ca, Ti and O-position of the cubic Perovskite.
In most cases the atomic coordinates feel no additional de- • edit of bonds
gree of fredom. If the threefold axis in case of P 4m mm will
• selection of parts of structure (molecules, single atoms
be excluded, only a splitting of the O position follows, i.e. we
etc.)
have 2 different, non-symmetry eqivalent O positions. However,
these two positions have no degree of freedom. Indeed, the lost 142
Alpo
P o w d e r C e ll 2 . 2

Alpo.x_y
symmetry generates an exclusive axis c, which is independent
from the lattice constant a. From this point of view also the
atomic positions vary so that the absolute atomic configuration
changes. 71

a)
Table 5
Wyckoff-splitting for Perovskites. The Wyckoff letter defines the position. The
j=-20
letter in brackets gives the degree of freedom, i.e. (z) means the coordinate can
vary in direction of z. If no bracket is given no degree of freedom exists for this 0
P o w d e r C e ll 2 . 2

atomic position. Except of the last transformation each case is described by a 155 20
Alpo
21 22 23 24 25

Alpo.x_y
translationengleiche subgroub I. The last one is a klassengleiche subgroup IIc.

P m3̄m I I I I IIc
P 4/m mm P 4mm C mmm P bnm P bnm
b)
78

Ca 1a 1a 1a (z) 2a 2a 4h (x,z)
j=0
Ti 1b 1d 1b (z) 2c 2c 2b
2c 0
P o w d e r C e ll 2 . 2

141 20 21 22 23 24 25
O 3c 1c 1b (z) 2b 2b 4h (x,z) Alpo
Alpo.x_y

2e 2c (z) 4f 4g (z) 4g (z)

4g (z)

71
A mixture between the two possibilities, changing lattice pa-
rameters and/or atomic position, occurs in case of P 4mm. All c) j=+20
atomic positions have the possibility to vary in z without chang-
ing the local symmetry but also the lattice constants a and c
0
can shift. In case of C mmm the relative atomic coordinates are P o w d e r C e ll 2 . 2

104 20 21 22 23 24 25

fixed, but now the lattice has the possibility to relax in all three Alpo
Alpo.x_y

directions: a, b and c. Please notice, that the unit cell has a twice
higher volume because of the C centration. If we reduce the
symmetry furthermore it is possible to describe the structure by
the space-group symmetry P bnm : the third setting of P mna. 52

However in this symmetry no structure is known. Experimen- d)

tally only a klassengleiche supgroup IIc of the same symmetry
is described by several authors (last column). The last column in
Tab.5 shows, that some positions can be changed whereas other 0

20 21 22 23 24 25
stay fixed. The Ca atom has even the ability to vary in x as well
in the z coordinate. This example shows, that subgroups rep-
resents a powerful tool for comparison of crystal structures or Figure 5
the investigation of phase transitions. However, there is not only Influence of the position of a C3 NH9 molecule within a cage of a zeolite. The
position of the molecule has been changed by rotation φ — a, b and c. In d) the
one path to a subgroup so that the analysis of subgroup relations
molecule has been deleted. The dots mark the calculated intensity of the correct
is sometimes more complicate than here demonstrated. crystal structure.
 The manipulation of crystal structure allows to study the in-
fluence of shifted or tilted structure parts on the powder pat-
tern. Unfortunately, the Wyckhoff symmetry cannot be fixed.
Therefore it is absolutely possible that the shift of an atom will
influence its multiplicity. Nevertheless this is a useful tool for
crystals with lower symmetry, e.g. the majority of organic com-
pound. In Fig.5 it is demonstrated for a zeolite containing an
organic molecule which has been rotated within the cage. The
dots represent the theoretical intensity curve resulting from the
actual crystal structure data. Now the position of the molecule
will be changed by rotation. The variation of the intensity curve
influenced exclusively by rotation of the molecule is shown as
single line. It seems to be that some reflections do not change
the intensity whereas other are strongly influenced. If the com-
plete molecule will be deleted we observe a drastic change of
diffracted intensity — Fig.5d).
4. Simulation of powder pattern
4.1. General remarks
Since the discovery of X-ray interferences in the beginning
of the last century the correct calculation of the reflection inten-
sities was an important task. From practical point of view the
quantitative phase analysis is one of the important problems.
Certainly, there the structure data must be known. In contrast to
the large group of scientists using e.g. this standard method only
a small number attend to the determination of crystal structure
data.
However, both groups use the same fundamentals for a cor-
rect calculation of reflection intensities. Nevertheless the meth-
ods are quite different because of the unknowns, respectively.
For the structure analysis only the relative intensities of a max-
imum of considerable reflections are necessary. If it would be
possible to exclude texture effects, in quantitative phase analy-
sis only a single reflection for each phase would be sufficient to
determine the fraction, respectively. But from the view of a bet-
ter reliability this is not acceptable. It is well known that even
the preferred orientation can have an essential influence on the
result of a quantitative phase analaysis.
Actually, the basic problem is to recognize which information
are necessary. From the view of structure analysis only the in-
tensity ratios must be known (and for a deconvolution the more
are available the better). For this case the well-known quadratic
relation between intensity and structure amplitude can be de-
scribed sufficiently using the simple equation for the structure
factor without further corrections. Therefore one finds the math-
ematical sign for proportionality between intensity and structure
amplitude.
However, it should be possible to calculate powder patterns of
mixtures under consideration of certain assumtions (e.g. compa-
2 The velocity of the neutrons is fixed by 2200 m/s. So a wavelength of 1.7982 results.
3 given in [barns/atom] / 10, International Tables for Crystalography, Vol.C, Tab. 4.2.4.2.
4 If the crystal is more similar to a perfect crystal i.e. there is approximately no mosaic structure the diffracted beams can be functioned as ”primary” beams. One
observes a lost of intensity which is called primary extinction. For a really perfect crystal the reflection intensity is equivalent to the absolute value of the structure
factor the structure amplitude. For the description of diffraction effects in perfect crystals the dynamic interference theory has been developed. However, usually
powders are not perfect crystals so that the more easy kinematic assumtions are sufficient for the calculation of reflection intensities. Only for semiconductors
dynamic formulations must be considered. On the other hand, if you use single crystals as monochromator you should be know the degree of perfectness.
rable grain-size distribution, degree of imperfections, homoge-
nization, preferred orientation etc.). Even in case of identical
experimental conditions comparisons of the diffraction power
of different materials are practicable, although die quantity and
the character of the unknown will be underestimated by the re-
searcher no rarely.
4.2. Intensity calculation
The calculation and representation of powder patterns is one
of the main features of PowderCell . The pattern can be evalu-
ated for a doublet of 11 different radiations (Cr, Mn, Fe, Co, Ni,
Cu, Zr, Nb, Mo, Ag and W). Furthermore neutron diffraction
experiments can be simulated2 .
For the simulation of X-ray diffraction pattern the atomic
scattering factors as well as the anomalous dispersion coeffi-
cients are necessarry. These are included for all radiation used
up to the atomic number 104 using FPRIME (Cromer & Liber-
mann, 1983). For the calculation of the mass attenuation the
total photon interaction cross section3 will be used. Unfortu-
nately the final atomic number which has been listed is 96. This
defines a limitation regarding the quantitative analysis of mix-
tures. For the radiations of Zr, Nb and W in principle no values
are given.
Natural crystals are characterized by a so-called mosaic
structure. This causes the higher divergence and the lower co-
herency of the reflected beam regarding to the incident beam.
The result is that the reflected beam will be emmited by the
crystal without a further diffraction. Thus the mosiac structure
represents the ideal case of a defect crystal4 (Massa, 1996). In
this case the intensity of an interference HKL is proportional to
the square of the structure amplidude |FHKL|:
IHKL = K · A · PLG · HHKL · |FHKL|2 (2)
where K is a constant, A represents the mass attenuation, PLG
describes the polarization, Lorentz and geometry correction and
FHKL is the structure factor. HHKL considers the reflection mul-
tiplicity. However, if a preferred orientation influence the inten-
sity HHKL must be substitute by OHKL.
The scaling factor K is a constant and enables e.g. the nor-
malization of the relative intensities regarding to the unit cell
volume and/or the mass (density). On this way it is possible to
analyse mixtures or to compare the scattering power of different
materials. Using A the influence of attenuation of the material is
considered. Normally, for a crystalline phase only relative inten-
sities will be determined and K and A can be neglected. How-
ever, for an analysis of the scattering power of a single phase A
has to be considered during calculation of intensity.
Usually the polarization, Lorentz and geometry factor will
be combined to a so-called PLG correction (sometimes it is de-
scribed as LPG or as LP correction (Allmann, 1994). Therefore,
very often complete PLG correction termes are listed in depen- sum of the product of g j and fij can be imagined as effective
dence of several focusing conditions or different constructions atomic scattering factor describing the position i in the struc-
of diffractometers (Yvon et al., 1977). In PowderCell the iden- ture.
tical corrections as in LAZY PULVERIX will be used. For the Because PowderCell is able to consider the anomalous dis-
Bragg-Brentano geometry the correction has the following de- persion the structure factor actually will be calculated by
pendency r
1 + cos2 2θ 2
fij◦ + ∆ fij + ∆ fij 2 ·
Pn Pn 0 00
PLG = (3) FHKL = i=1 j=1 ki g j
sin2 θ cos θ
The multiplicity HHKL of a lattice plane {hkl} defines the num-   00
 (7)
∆f
ij
ber of all symmetry-equivalent lattice planes. On the one hand − 2πi(Hxi +Kyi +Lzi )+arctan
f ◦ +∆ f
0

it depends from the indexing of the lattice plane itselfs, on the
other hand the given number of all lattice planes are charac-
teristic for the point-group symmetry, respectively. Normally,
the multiplicity will be used to decrease the processing time,
because for all symmetry-equivalent lattice planes (or interfer-
ences) all properties (in our case the diffracted intensity) are
identical5 . If the probability for the occurence for each indi-
vidual (hkl) of {hkl} is not the same this must be considered
additionally using the correction factor OHKL. This is described
by different models. A very simple was developed by March
(1932) and will be used in other Rietveld programs, too. Mainly
it is useful for the description of the preferred orientations of ax-
ial crystals.
3
H 
sin2 ϕi 2
X 
2 2
OHKL = o cos ϕi +
i=1
o
This equation has the advantage to contain the increase as
well as the decrease of intensity caused by a preferred orienta-
tion. The degree of it will be adapted by o. Furthermore, it is
in general use in Rietveld programs to determine the fractions
of multiphase mixtures. The most important disadvantages are
the limited validity for crystals with lower symmetry. Addition-
ally, for crystals with higher symmetry (e.g. the axial crystal
systems) a general description about the full 2θ range is nearly
impossible regarding a constant o.
PowderCell uses also other models which are more powerful
in case of application for crystal structure analysis (Toraya &
Marumo, 1981; Sasa & Uda, 1976). If quantitative phase anal-
ysis is in the focus of interest these models are unsuitable.
The structure factor FHKL is implemented in PowderCell
using the following equation:
n X
X n
FHKL = ki g j fij exp−2πi(Hxi+Kyi +Lzi ) ·Tiiso
j (5)
i=1 j=1
in which the isotropic temperature factor will be described by
 2
sin θ
−Bi j
Tiiso = exp λ .
j
ki is the occupation factor, g j is the substitution and fij describes
the atomic scattering factor. At first it will be summarized about
all atoms j of one and the same atomic position (x, y, z)i . The
5Though, only the absolute necessary part of reciprocal space must be considered during the generation of the reflection. The size of the considered space is defined
by the point-group or Laue-group symmetry of the given crystal structure. This presupposes a homogeneous orientation distribution of the crystallites.
· exp ij ij
·Tiiso
j
were fij◦ is the atomic scattering factor and ∆ fij and ∆ fij are cor-
0 00
rection terms of fij◦ considering anomalous dispersion effects.
fij◦ itself will be approximated using the dependency described
from Cromer & Mann (1968):
4 sin2 θ
X −bjq 2
fij◦ (sin θ/λ) = ajq · exp λ +c j . (8)
q=1
The aij , bij and c j has been calculated by M. Wendschuh-Josties
using FPRIME (Cromer & Libermann, 1983).
4.3. Convolution of line intensities
(4) PowderCell uses symmetric model functions for the convolu-
tion of calculated intensities: Gaussian, Lorentz, Pseudo-Voigt1
and Pseudo-Voigt2. The area content of these curves is normal-
ized to 1. The used functions are well known and will be ap-
plied also in other Rietveld programs (Izumi, 1987). The first
three have no free parameter, except of the full width at half
maximum (FWHM) whereas the Pseudo-Voigt2 is defined by
two which have to refined manually or automatically.
The change of peak width FWHM in dependence of the
Bragg angle θ is considered by the Caglioti formula (Caglioti
et al., 1958):
FWHM2 = U tan2 θ + V tan θ + W. (9)
U, V and W are free parameter which also have to fit. For small
angle ranges it seems to be sensible to refine W only and if this
describes in average the peak width quiet good, U and V can be
switched on too.
5. Refinement
There is no doubt that the refinement procedure in PowderCell
improved the quality of the program especially from the practi-
cal point of view. The calculation of the correct line intensity is
the one hand. The other hand is the ability to compare a exper-
(6) imental diffractogram with the theoretical one. It is clear that it
is really difficult to adapt the several parameters manually: scal-
ing factors, zero shift, background polynom, lattice parameters,
profile parameters and preferred orientation. So an automati-
cal refinement has been implemented where also limits can be
set. The dialog window for the lattice and profile parameters is For more detailed information The Rietveld Method edited by
shown in Fig.6. Young (1993) and the monograph Modern Powder Diffraction
edited by Bish & Post (1989) are recommended.

5.1. Quantitative phase analysis

To use PowderCell for quantitative phase analysis, the right
intensity correction must be used. In phase options for the nor-
malization I = I◦ /(VEZ · m) must be used6 to get the result in
mass%.
Let us assume we get a mixture between the two TiO2 -phases
— Rutile and Anatase. The fraction of Rutile shall be deter-
mined using powder diffraction.
At first we need the crystal structure data from both phases.
Usually the powder pattern will be calculated by PowderCell
using a constant FWHM. The resulting diffractograms and the
experimental powder pattern are given in Fig.7. Because of the
large angle range it is recommended to reduce the 2θ-range to
20◦ − 80◦ .
Figure 6
The dialog window for definition of refinement parameters.

For each considered crystalline phase the independent lattice

constants, the profile parameters and the preferred orientation a)
can be selected as to refined. On other work sheets the general
settings (zero shift, background etc.), the refinement of atomic
coordinates, the reached results and the standard settings of for
the initial refinement parameters can be adjusted. As visible in
Fig.6 the refinement paramaters will be activated by setting a
tick. All other don’t will be varied during the refinement proce-
dure.

b)

c)
Figure 7
Experimental and simulated diffraction pattern for a unknown mixture of Rutile
and Anatase. Therefore both phases are described by the half, respectively. The
Peak width are calculated using a constant default value.

In dependence of the quality of experimental data but also of

the number of different phases the refinement seems to be very
complicate or needs experience in interpretation of refinement Figure 8
steps. Therefore a set of rules has be given by McCusker et al. Refinement step by step. a) Only W and some general parameters are active.
b) In a second step the U and V are switched on but also the preferred orienta-
(1999) which should be noticed by beginners. There also the
tion of Rutile. c) At the end also a preferred orientation for Anatase has been
several influences on peak shape and differences are described. offered, but the effect is very low and has no influence on the phase fraction.
6 The correct term is I = I◦ /(VEZ2 · ρ) = I /(V 2
◦ EZ · m) where ρ is the X-ray density. The division by the unit cell volume VEZ results from the derivation of the
structure factor from the electron density deviation function, where the volume represents only a proportional term and will be neglected. Since the structure factor
will be considerd within the intensity calculation in form of the quadratic of the structure amplidude, also the unit cell volume must be considered in a quadratic
form. The X-ray density correction enables only the use of mass% inspite of vol%. Even for selfmade mixtures the weight fraction is better known than the volume
fraction of the several phases.
 The simulated diffraction pattern described the peak posi-
tions quiet good. Only a small peak shift is visible and, of
course, the peak widths don’t agree among eatch other. At the
first step the background shall be fitted, the constant part of the
peak width W , the lattice parameters of both phases, the zero
shift of the powder pattern7 and the scale factors which de-
scribe the phase fractions8 . Therefore all other parameter must
be switched off. The result of a three cycle refinement is shown
in Fig.8a). The background fitted by a polynom of 7th degree
is represented acceptable. However the peak widths of the re-
flections are to small at higher angles, especially for Anatase.
PowderCell allows to display the difference plot of experimen-
tal and simulated data. This is shown in Fig.8b). There all pa-
rameters have been switched on, i.e. all phase specific but also
general variables. Additionally, for Rutile a preferred orienta-
tion has been assumed to reduce the intensity of the reflection
110. The result is only a small change in mass fraction but a bet-
ter agreement with the experimental curve, visible by the differ-
ence plot. Finally, also for Anatase a preferred orientation has
been arranged because the 200 couldn’t describe satisfying but
actually no effect could be observed — see Fig.8c).
In Fig.8 the single diffraction pattern will be shown but no
sum of theoretical curves. In that case this is no grave disad-
vantage because the reflections are mostly separated and there-
fore this example is comparatively easy. However, it shall show
only the possibilities of PowderCell . On the other hand, in-
stead of the sum of single curves the difference plot gives a
much better overview about the quality of refinement. In spite
of the good agreement between simulated and experimental pat-
tern one should notice, that also after the first step the phase
fraction varies only slightly.
a)
b)
Figure 9
Refinement of the complete measurement. For a better resolution the inten-
sity scale has been increased. a) shows the result including the background.
b) represents the superposition (sum of both theoretical diffractograms) with-
out background. The fitting region has been enlarged because at the end of the
angle range measured the influence of a reflection can be observed.
7 This is caused by a wrong 2θ-position of the detector.
8 Always under the preassumption that the mixture contains only crystalline materials. If we consider the strong background we have to admit that this is not correct.
Now it is time to use the complete data set, i.e. step by step
the angle range can be increased. In that case you will see that
the background description is usually valid only for the limited
angle region. Therefore the background must be deleted com-
monly. This procedure improves the quality of refinement, es-
pecially of the 2θ-dependent broadening of reflection. In Fig.9
the final refinement is shown.
At first it one can recognize that the assumed symmetric pro-
file function doesn’t describe the shape of reflection absolutly.
Furthermore it seems to be that also the used profile function is
not optimal. However, the agreement between experiment and
simulation is acceptable good. The angle range of the consid-
ered theoretical powder pattern has been enlarged that also re-
flections are considered which are not in this range but influence
this.Differently it would be interpreted as background.
In Fig.9b) the sum of the theoretical curves of both phases
without background polynom is represented. Thus, it is very
impressive to see the correspondence between the course of the
experimental and the theoretical powder pattern.
5.2. Size and strain
Using PowderCell it is also possible to determine size and
strain. The theory implemented is given by Klug & Alexan-
der (1974). For this aim the method of integral breadths will
be used. However, instead of the integral breadths FWHM will
be used.
a)
b)
Figure 10
Refinement of the complete measurement. For a better resolution the inten-
sity scale has been increased. a) shows the result including the background.
b) represents the superposition (sum of both theoretical diffractograms) with-
out background. The fitting region has been enlarged because at the end of the
angle range measured the influence of a reflection can be observed.
 If one defines L as the mean dimension of the crystallites
composing the powder, λ as the wavelength used, K as a con-
stant approximately equal to unity9 , θ◦ as the position of the
peak maximum and e ' (∆d/d) ¯ hkl as an approximate upper
limit of the lattice distortions a linear dependency can be given:

FWHM2
 
Kλ FWHM
2
= + 16e2 (10) a)
tan θ◦ L tan θ◦ sin θ◦

which allows to determine the crystal size from the slope af the
line. The origin intercept describes the lattice distorsion e.
This dependence is also very useful for the interpretation of
the refined U, V and W because these values define the course of
the FWHM. In Fig.10a) the reflections of Rutile are represented
as small crosses and the line is given as linear approximation.
It shows that for small (FWHM)/(tan θ◦ sin θ◦ ) the coincidence
between the crosses and the fitted line is acceptable but could be
better. However, if the refinement of U, V and W is unfavourable
a strong disagreement can be observed in the size and strain
fitting. The coincidence for Anatase inFig.10b) is much better
and indicates a good reliability of the refined U, V , and W . Of
course, if the powder is characterized by a strong anisotropy of
crystal size and/or lattice strain the preassumptions for the use
of (9) and (10) are incorrect and this model cannot be used.
5.3. Deconvolution — a Le Bail likely method
Usually PowderCell needs all structure data and lattice pa-
rameters to be able to work. However, what one should do if no
structure data are available or unknown? In former times struc-
ture factors have been extracted by hand, e.g. cutting peaks on
the recorded paper and weighting them or using a planimeter.
In the beginning of the 70th of the last century peaks have been
approximated as triangle (Fayos & Salvador-Salvador, 1971).
Nowadays, mostly the Le Bail (Le Bail et al., 1988), Pawley
(?) and Rudolf and Clearfield methods are used. The Le Bail
algorithm persuades by a better stability and a faster execution.
A similar method has been included in PowderCell . It shall
be explained by an example: UU2 (H2 AsO4 )2 ·H2 O. For the ap-
plication in PowderCell the lattice parameters and at least the
Laue group describing the multiplicities are necessary. If the
space-group type can be extracted it is more reliable because
of the use of extiction laws. So it was known: ao = 13.156Å,
bo = 8.853Å, co = 9.046Å, β = 124.53◦ and space-group type
C 1 2/c 1 (space-group number: 15).
The deconvolution starts using a fixed structure amplitude (in
PowderCell = 100) for each reflection. Thus, the intensity of re-
flection will be determined exclusively by the multiplicity of re-
flections and the PLG correction. The result of this assumption
is shown in Fig.11a). Because the difference between experi-
mental and theoretical curve is comparatively big no difference
plot has been given. After three cycles of deconvolution and re-
finement the agreement is surprisingly good. Beside the fitting
of intensities also the lattice parameter have been refined. These
are listed in Tab:6
9 It is common practice to set K equal to unity.
b)
Figure 11
Refinement of an X-ray powder pattern. The Background has been substracted
before. a) The first simulation of the powder pattern uses fixed structure fac-
tors for each reflection. b) After threefold deconvolution and refinement a good
agreement between experimental and theoretical data has been found.
Table 6
Lattice parameter before and after refinement.
ao bo co β
initial 13.156Å 8.853Å 9.046Å 124.53◦
refined 13.170Å 8.859Å 9.053Å 124.48◦
All structure amplitudes will be written in input files for
SHELX: one structure file (∗.ins) and one file containing
the reflection indexing and the adapted structure amplitudes
(∗.hkl). Now SHELX can be used to separate the crystal struc-
ture or segments of it from these data. Repeating this procedure
the selected of atomic positions by SHELX describe the powder
diffraction pattern better reliable so that the refinement works
more reliable.
Except for crystal structure analysis the convolution can be
used also for a lattice parameter refinement how Tab.6 shows.
6. Conclusions
PowderCell is a program which can be used for different ap-
plications. It is a tool for practical work but also for crystal-
lographers, which are interested in subgroups and their appli-
cation on scientific questions. Especially the simple input files
and the low level knowledge allows also non-specialists to work
with this program. The combination of structure vizualisation
and powder pattern generation offers an intuitive working mode
which is supported by a user-friendly shell. In spite of the rela-
tive simple profile functions used the refinement procedure is an
acceptable feature for qualitative or quantitative phase analysis.
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