132
218 (2003) 132143
Structural analysis of complex materials using
the atomic pair distribution function a practical guide
Th. Proffen*, I, S. J. L. BillingeII, T. EgamiIII and D. LoucaIV
I
Los Alamos National Laboratory, LANSCE-12, MS H805, Los Alamos, NM 87545, USA
II
Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824-1116, USA
III
Department of Materials Science and Engineering, University of Pennsylvania, Philadelphia, PA 19104, USA
IV
Department of Physics, University of Virginia, Charlottesville,VA 22901, USA
Received July 29, 2002, accepted November 11, 2002
Abstract. Modern materials and their properties are of-
ten characterized by varying degrees of disorder. Routine
crystallographic structure solution only reveals the average
structure. The study of Bragg and diffuse scattering yields
the local atomic arrangements holding the key to under-
standing increasingly complex materials. In this paper we
review the pair distribution function technique used to un-
ravel the local structure. We aim to give a practical over-
view and make this method easily accessible to the wider
scientific community.
Introduction
In the past 50 to 100 years our knowledge of materials
has been revolutionized by the ability to determine the
atomic structure of increasingly more complex materials.
In more recent years biology is experiencing the same re-
volution powered by the advances in the field of protein
crystallography. The best way to accurate crystallographic
structure determination is single crystal diffraction. How-
ever, in many cases only poor quality single crystals can
be grown or even worse the material of interest is not
forming single crystals of the required size at all. In these
cases powder diffraction is the method to choose and this
technique has also matured over the last 30 years or so.
The breakthrough in powder diffraction data analysis came
with the Rietveld method (Rietveld, 1969). Here the full
profile of the powder diffraction pattern is refined based
on a structural model. Rietveld techniques have been im-
proving dramatically, with the recent successful refine-
ments protein structures (von Dreele et al., 2000; von Dreele,
2001) being proof of that.
With increasing complexity of materials, the traditional
crystallographic structure solution approach is no longer
sufficient to understand properties of materials on an
atomic scale. The limitation of traditional structure refine-
ments is of course the fact that it only yields the long
range average structure of the material. Figure 1 illustrates
* Correspondence author (e-mail: tproffen@lanl.gov)
Z. Kristallogr.
# by Oldenbourg Wissenschaftsverlag, Munchen
this point. The top panels show two simulated structures,
both having the same lattice with one atom per unit cell as
well as the same concentration of vacant sites. What is
different is the ordering: Panel (a) shows a random distri-
bution whereas in panel (b) we see chemical short range
order (SRO), in this case vacancies prefer to be arranged
in chains along the x- and y-direction. The powder diffrac-
tion patterns for both structures are shown in Fig. 1c. Ana-
lysis of the Bragg scattering e.g. using the Rietveld meth-
od will yield identical results for both structures since
Bragg peak positions and intensities are the same. This is
indeed no surprise since the average structure of both
structures is identical with a site occupancy of 70%. The
inset of Fig. 1c shows the powder pattern magnified by a
factor of 100 and we observe a difference in the diffuse
scattering for the two structures. Fig. 1d shows the corre-
sponding PDFs. Since the total scattering pattern is used,
the PDF is sensitive to the chemical SRO as can be read-
ily seen from the difference curve plotted below the
curves in Fig. 1d. In summary we note that Bragg scatter-
ing contains information about the long range average
structure whereas diffuse scattering contains information
about in general two-body correlations, in this example
about the chemical SRO. However two-body correlations
can not only be chemical SRO but also distortions, corre-
lated motion or orientational SRO of molecules to name a
few examples.
As we have stated before, determining the atomic ar-
rangements holds the key to understanding and possibly
predicting properties of materials. It is easy to imagine
that the particular vacancy ordering in Fig. 1 is determin-
ing the properties of that material. Clearly one needs to go
beyond the analysis of Bragg scattering or beyond tradi-
tional crystallography to study the local atomic structure
based on the total scattering pattern, which includes Bragg
and diffuse scattering. Again the most information about
disorder in a crystal can be obtained via analyzing single
crystal diffuse scattering. More information about this to-
pic can be found in numerous review articles (e.g. Frey,
1997; Welberry and Butler, 1994) or a recent book by
Nield and Keen (2001). However, significant, and often
sufficient, information can be gleaned from total scattering
Structural analysis of complex materials

a 
b

c 7.1


d
Fig. 1. (a) shows a random distribution of vacancies and (b) pre-
ferred ordering in x- and y-direction. Panel (c) shows the correspond-
ing powder diffraction patterns. The inset shows the background en-
larged by a factor of 100. Panel (d) shows the corresponding PDFs
for the random distribution (filled circles) and the short-range ordered
distribution (solid line). The difference is shown below.
powder measurements, as we discuss below, and experi-
ment as well as data analysis are in general less com-
plicated. In this paper we focus on the analysis of the
atomic pair distribution function (PDF) obtained from the
total scattering from powder samples. In fact the PDF
method was originally applied to the study of liquids and
amorphous materials but can also be applied to disordered
crystalline materials (Egami, 1990). The strength of this
approach is that it can be applied to the complete spec-
trum of materials from non-crystalline materials to crystals
with varying degrees of disorder on various length scales.
Obviously this also includes the very important group of
nano-materials.
In this paper we will try to give a practical guide to the
PDF method focussing on the use of neutron diffraction.
However, most of the presented material applies equally
well to X-ray diffraction, especially using high energy
synchrotron radiation. Also we will limit the examples to
disordered crystalline materials. Further reading on the
technique and its applications can be found in Billinge
and Thorpe (2002, 1998) and in a recent book by Egami
and Billinge (2002). For more information as well as ac-
cess to software visit http://www.totalscattering.org.
133
7.1 A
o

a 
c

b 
d
Fig. 2. C60 (a and b), its normalized neutron diffraction pattern (c)
and the corresponding PDF (d). The vertical dotted line in (d) is at
A the diameter of the ball (from Billinge et al., 2000a).
PDF basics
In this section we will discuss some basics of the PDF
analysis method: what is a PDF, how to obtain one and
finally what can be learned from an experimental PDF.
What is a PDF?
The PDF gives the probability of finding an atom at a given
distance r from another atom. In other words it can be un-
derstood as a bond length distribution. In some sense the
PDF is similar to the Patterson function well known to
crystallographers, but one has to be be aware that normally
the Patterson function will only give interatomic vectors
within a unit cell corresponding to the average structure
since only Bragg intensities contribute to the Fourier trans-
form. The PDF on the other hand is obtained via the Fourier
transform of the total scattering pattern and yields the local
structure on length scales beyond the unit cell size.
The study of the PDF on different length scales allows
one to obtain information about the nano-scale structure of
materials. For example, consider the PDF from a sample
that has some kind of domain structure with a characteris-
tic domain size of x. This is illustrated in Fig. 2. Looking
at the PDF on a length-scale
x the pairs of atoms con-
tributing will predominantly lie within the same domain as
each other and the resulting structure will be the intra-do-
main structure. Studying the same PDF at a distance
r > x=2 then most of the pairs of atoms giving rise to
features in the PDF lie in different domains and the result
is the average of the different local structures. This is no-
where better illustrated than if we think of solid C60 as a
microstructured material where each bucky ball is a single
domain. The bucky ball, its scattering and PDF, are shown
in Fig. 2. The diameter of the ball is 7.1
A. Sharp peaks
are observed in the PDF coming from the characteristic
CC pairs on the ball up to 7.1
A. Thereafter only broad
featureless structure exists. The sharp peaks are the intra-
molecular structure and the broad feature the inter-molecu-
lar structure, or ball-ball correlations.
134 Th. Proffen, S. J. L. Billinge, T. Egami et al.

Fig. 3. PDF, Gr, of Ni obtained from GLAD instrument at IPNS range extends to r 100
A. The scattering data were terminated at
(filled circles) and NPD at LANSCE (solid line). Note the displayed Qmax 35
A1 for both data sets.

How to obtain a PDF? of research. Compared with the XAFS technique which is
capable of determining only the first and second nearest
The PDF is obtained from the powder diffraction data via neighbor distances, the PDF method has an advantage of
a sine Fourier transform of the normalized scattering inten- describing the short- as well as medium-range local struc-
sity SQ: ture. Currently a high resolution neutron powder diffract-
Gr 4prqr  q0  ometer, NPDF, is being constructed at the Lujan Center at

1 LANSCE (Proffen et al., 2002a). This diffractometer is an
2 upgrade of NPD and will be dedicated to PDF studies in
QSQ  1 sin Qr dQ ; 1 particular or materials where the medium-range order is of
p
0 interest. With the proposal of a disordered materials dif-
where qr is the microscopic pair density, q0 is the aver- fractometer at the Spallation Neutron Source (SNS) cur-
age number density and Q is the magnitude of the scatter- rently being constructed, the future for PDF type studies is
ing vector. For elastic scattering Q 4p sin q=l with 2q looking very promising. Similar efforts are under way to
being the scattering angle and l the wavelength of the build a dedicated X-ray PDF beamline at the Advanced
radiation used. Photon Source in Argonne National Laboratory.
The trouble with the Fourier transform is that we Having done the experiment, the remaining challenge
would like to measure our data up to Q infinity which of is to obtain the properly corrected and normalized struc-
course is not possible. The cutoff at finite Q decreases the ture function SQ which is then Fourier transformed. For
real space resolution of the PDF and causes so called ter- X-ray scattering, data processing software choices include
mination ripples. The decreased resolution in the PDF is
illustrated in Fig. 4. Here we see the nearest neighbor
peak of the semiconductor alloy ZnSe0:5 Te0:5 terminated at
two different maximum values of Q. The interesting fea-
ture in these alloys is the difference in bond lengths for
ZnSe and ZnTe of Dr 0:14
A. The PDF obtained
from the data terminated at Qmax 40
A1 clearly shows
the two distinct bond lengths. However if the same data
are terminated at Qmax 17
A1 only one broad peak is
observed in the PDF. This cutoff corresponds to using
MoKa radiation. Even though for some applications the
use of a laboratory X-ray source might yield useful PDF
data, in many cases high energies are required to be able
to access high values of Qmax . In the case of X-rays this
requires the use of high energy synchrotron radiation. For
neutron PDF measurements spallation neutron sources are
the most suitable. The influence of the resolution in reci-
procal space, DQ on the PDF can easily be seen by in-
specting Fig. 3 showing Gr for nickel. In all cases the
data were terminated at Qmax 35
A1 . Note that the
PDF in Fig. 3 extends out to r 100
A. The Q resolution Fig. 4. PDF around the nearest neighbor peaks of ZnSe0:5 Te0:5 . The
results in an exponential dampening of the PDF peaks as A1 clearly show-
solid line corresponds to terminating at Qmax 40

ing the two bond length ZnSe and ZnTe which differ by
function of r (Toby and Egami, 1992). Using high Q-reso- Dr 0:14
A. The dotted line shows the PDF obtained from the same
lution data for PDF analysis allows one to access medium data terminated at Qmax 17
A1 . In this case the peak split is
range distances, 10  100
A, opening up a new territory smeared out.
Structural analysis of complex materials
PDFgetX (Jeong et al., 2001) and RAD (Petkov, 1989).
These programs perform background substraction, absorp-
tion and multiple scattering corrections as well as normal-
ization and removal of Compton scattering contributions.
Neutrons are used for quite some time for PDF studies of
glasses and liquids and the two main data processing
packages are the GLASS package (Price, undated) and the
ATLAS package (Soper et al., 1989). These packages are
also used to process data obtained from crystalline materi-
als. More recently a user-friendly interface, PDFgetN, to
the GLASS package has been developed to make data pro-
cessing available beyond the circle of specialists (Peterson
et al., 2000). It can be difficult, especially for the non-spe-
cialist, to judge the quality of a resulting PDF or to main-
tain conditions when processing a large number of PDFs
which were collected e.g. as a function of temperature.
The program PDFgetN also offers a set of quality criteria
to aid in these questions. More details can be found in
Peterson et al. (2002).
So far we have talked about the total PDF, where all
atoms in the sample contribute. By changing the scatter-
ing power of one or more elements it is possible to ex-
tract a chemically specific PDF. In a binary alloy two
measurements contrasting atom B would yield the differ-
ential PDF containing contributions from AA and
AB pairs. Using three independent measurements, all
partial PDFs AA, AB and BB can be extracted. Monte Carlo technique (McGreevy and Pusztai, 1988) can
For X-ray scattering one utilizes the fact that close to the
absorption edge of a specific element the scattering
power changes due to anomalous scattering. An example
of the chemically specific PDF of the semiconductor al-
loy In0:5 Ga0:5 As is given in Petkov et al. (2000b). In
case of neutrons one can use the fact that different iso-
topes of an element have different neutron scattering
length. Isotope substitution studies are applied to glasses
and liquids (e.g. Petri et al., 2000; Dixit et al., 2002) but
are also used to study disordered crystals, e.g. in a study
by Louca et al. (1999) on high temperature superconduct-
ing cuprates.
Modelling of a PDF
After having obtained an experimental PDF, the question
arises how to analyze it. The simplest analysis is to obtain
bond length information and coordination numbers by fit-
ting the near neighbor peaks of the PDF. A simple analy-
sis of the peak width reveals information about correlated
motion (Jeong et al., 1999). However, in most cases the
comparison or refinement of a structural model will de
desired. The PDF is simply the bond length distribution of
the material weighted by the respective scattering powers
of the contributing atoms. The PDF can be calculated
from a structural model using the relation
" #
1 P P bi bj
Gc r dr  rij  4prq0 ; 2
r i j hbi2
where the sum goes over all pairs of atoms i and j within
the model crystal separated by rij. The scattering power of
atom i is bi and hbi is the average scattering power of the
135
sample. In the case of neutron scattering bi is simply the
scattering length, in the case of X-rays it is the atomic
form factor evaluated at a given value of Q. For Q 0 the
value bi is simply the number of electrons of atom i. To
account for the limited range in Q, the calculated function
Gr is then convoluted with a termination function,
sin Qmax r=r. We find this approach to be more reliable
than to introduce a termination function in the Fourier
integral (Eq. 1). Similarly the effect of the resolution in
reciprocal space is modelled by multiplying the calculated
PDF with a exponential dampening function (see Toby
and Egami, 1992).
Full profile refinement of the PDF based on a structur-
al model can be carried out using the program PDFFIT
(Proffen and Billinge, 1999). The program allows to re-
fine structural parameters such as lattice parameters,
anisotropic atomic displacement parameters, position and
site occupancies. Even though this is similar to the results
of a Rietveld refinement, one needs to realize that the
structural model obtained is strictly only valid for length
scales corresponding to the r-range used for the refine-
ment. This opens up the possibility to study the local
structure on different length scales by varying the r range
refined (Egami, 1995). This approach works very well in
situations where the model structure can be described
with relatively few atoms. In other cases the Reverse
be used to match a structural model containing many
atoms to an experimental PDF. A comprehensive sum-
mary of the method applied to crystalline materials is
given in Tuker et al. (2001a). The algorithm works as fol-
lows: First, the PDF is calculated from the chosen crystal
starting configuration and a goodness-of-fit parameter c2
is computed.
PN G r  G r 2
e i c i
c2 : 3
i1 s2
The sum is over all measured data points ri , Ge stands for
the experimental and Gc for the calculated PDF. The RMC
simulation proceeds with the selection of a random site
within the crystal. The system variables associated with
this site, such as occupancy or displacement, are changed
by a random amount, and then the model PDF and the
goodness-of-fit parameter c2 are recalculated. The change
Dc2 of the goodness-of-fit c2 before and after the gener-
ated move is computed. Every move which improves the
fit (Dc2 < 0) is accepted. Bad moves worsening the
agreement between the observed and calculated PDF are
accepted with a probability of P exp Dc2 =2. A com-
prehensive study on cristobalite using the RMC technique
was done by Tucker et al. (2001b). The PDF is also sensi-
tive to chemical SRO similar to the example in Fig. 1. The
feasibility of extracting chemical SRO parameters from
PDF data was shown by Proffen (2000) using simulated
data. The reader might refer to that paper for more details
on the RMC refinements. More recently SRO parameters
for Cu3 Au were successfully extracted from measured
PDF data (Proffen et al., 2002b). These studies were car-
ried out using the defect structure simulation program
DISCUS (Proffen and Neder, 1997).
136
Applications
In this chapter we present a very subjective list of applica-
tions of the PDF method to study the local structure.
Again it should be mentioned that there is an extensive
range of PDF studies on amorphous materials and liquids
which are beyond the scope of this paper.
Strain in semiconductor alloys
The first application of the PDF technique we like to dis-
cuss is the study of local atomic strain in semiconductor
alloys, A1x Bx C. The technological interest in these mate-
rials is given by the fact that the band gap can be tuned as
function of the composition x. The so-called IIIV semi-
Th. Proffen, S. J. L. Billinge, T. Egami et al.
of the time. The data were processed using PDFgetN
(Peterson et al., 2000). The reduced structure functions,
QSQ  1, obtained from the ZnSe1x Tex samples are
shown in Fig. 5 and the corresponding PDFs are shown in
Fig. 6. Some conclusions can be draw from simple inspec-
tion of the PDFs shown in Fig. 6. Let us focus first on the
area between the vertical dotted lines labelled (L) in the
figure. As we start from the bottom (x 0) we see the
ZnTe NN peak decrease in height and the SeTe NN peak
increase as a function of composition. It can also be
clearly seen that the corresponding bond lengths stay close
to their respective end member values. This will be com-
pared to XAFS results below. The region labelled (L) re-
flects the local structure. The situation is different in the
area between the vertical dotted lines labelled (A) in
conductor alloy ZnSe1x Tex can be made over the entire
range of compositions. Looking at the crystallographic
structure, we find that both end members ZnTe and ZnSe
have the zinc-blende structure (F 43m) with Se/Te occupy-
ing (0, 0, 0) and Zn occupying (1=4 1=4 1=4). The lattice
parameter of the alloys interpolates linearly between the
end member values as function of the composition, x, con-
sistent with Vegards law (Vegard, 1921). Conventional
structure analysis also results in nearest neighbor (NN)
bond length interpolating between the respective end
member values. However, theory (Cai and Thorpe, 1992a,
b) shows that the atomic NN distances stay close to their
natural lengths found in the end-member compounds:
L0ZnTe 2.643(2)
A and L0ZnSe 2.452(2)
A. This is
confirmed by X-ray absorption fine structure (XAFS) ex-
periments (Boyce and Mikkelsen, 1989). XAFS is also a
local structural probe, however in contrast to PDF it is
limited to the nearest and second nearest neighbor shells.
More recently the PDF method has been used to study the
local structure of Inx Ga1x As (Petkov et al., 1999, 2000b).
Fig. 6. Here we observe the two peaks around r  7
A
shift to larger distances as the value of x increases. We do
not observe peaks appearing and disappearing as for the
NN peaks. In this region we observe the Vegards law be-
havior of the average structure However, it is also clear
that the PDF peaks broaden for intermediate compositions
which indicates large static displacements caused by strain
in the alloys. The NN peaks were characterized by profile
fitting (for details see Peterson et al. (2001)). The resulting
NN bond length and their 2s error bars are shown as
filled circles in Fig. 7. The values determined from an
XAFS study by Boyce and Mikkelsen (1989) are shown
as empty circles in the same figure. There is excellent
agreement between the results.
Since the bond length differences are only 0.10.15
A,
high energy X-rays were needed for this study in order to
obtain the required value of the maximum momentum
transfer needed to resolve the NN peaks, as we have seen
in the previous section and Fig. 4.
The example given here is a neutron PDF study of the
semiconductor alloy ZnSe1x Tex (Peterson et al., 2001).
Time of flight neutron powder diffraction data were meas-
ured on the GEM diffractometer at the ISIS spallation
neutron source at Rutherford Appleton Laboratory in
Oxfordshire, UK. This instrument yields useful diffraction
information up to a maximum Q of greater than 90
A1 .
Unfortunately, due to a neutron resonance in Te, the Four-
ier transform need to be terminated at a maximum Q of
40
A1 in this experiment. This resulted in NN peaks in
these alloys which are resolution limited rather than sam-
ple limited. This was verified by Fourier transforming the
ZnSe end-member at higher values of Qmax . The NN peak
kept getting sharper up to Qmax 60
A1 . Nonetheless,
the distinct short and long bond distances are still evident
in the alloy PDFs. The total measuring time per data set
was only 60 min in comparison to 12 h for X-ray data of
similar quality. It should also be noted that at the time of
the measurement the backscattering detector banks on Fig. 5. Normalized reduced structure function FQ QSQ  1
GEM were not operational. With the present instrument of ZnSe1x Tex . Measurements were carried out on GEM diffract-
GEM, similar quality PDFs can be obtained in a fraction ometer at ISIS at T 10 K (from Peterson et al. (2001)).
Structural analysis of complex materials
Fig. 6. PDF, Gr, of ZnSe1x Tex obtained from diffraction data
show in Fig. 5 (from Peterson et al., 2001). More details see text.
Models for realistic alloy structures can be obtained
using the Kirkwood potential (Kirkwood, 1939). The Kirk-
wood potential is given by
 
a P b P 1 2
V Lij  L0ij 2 L2e cos qijk ; 4 meters are needed to obtain the model PDFs for the com-
2 ij 8 ijk 3 plete compositional range. The observed and calculated
Fig. 7. NN positions from the PDF (*) (Peterson et al., 2001), XAFS
data (Boyce and Mikkelsen, 1989) (*), and Kirkwood model z-plot
(solid line) (Cai and Thorpe, 1992b) as a function of composition, x,
for ZnSe1x Tex . The dashed line is the average NN distance. Note
that not all XAFS points had reported error bars so they were all set
to the same value (from Peterson et al., 2001).
137
Fig. 8. Comparison of Kirkwood model result for ZnSe0:5 Te0:5 (solid
line) with experimental data (*). The difference is plotted below the
curves, the dashed lines correspond to an error of 2s (data from
Peterson et al., 2001).
where L2e is the NN bond length of an undistorted refer-
ence crystal structure, Lij is the length of the bond be-
tween the atoms i and j, and L0ij is the natural bond-length.
In this definition the bond-stretching, a, and bond-bend-
ing, b, force constants have the same units and
qijk arccos  13, for an ideal tetrahedron. The details of
the modelling procedure are given in Cai and Thorpe
(1992a, b); Chung and Thorpe (1997, 1999). The values
for the potential parameters a and b can be obtained from
the PDFs of the end members. The derived slopes for the
NN bond lengths are shown as solid lines in Fig. 7. Once
the values for a and b are established, no further para-
PDF for x 0:5 is shown in Fig. 8. From these results it
is clear that the PDF is an excellent tool to extract local
bond length information even in cases where the mismatch
is only about 0.10.15
A. Furthermore, the comparison to
results based on a Kirkwood model with no adjustable
parameters over a wider range in r clearly demonstrates
the quality of the PDFs extracted. One should keep in
mind that one can obtain such a data set on modern
neutron scattering machines such as GEM in less than
30 minutes.
Local structure of doped manganites
A large class of exotic oxides with remarkable properties
are based on the perovskite structure and have the chemi-
cal formula ABO3 . Examples include high temperature
superconductors, ferroelectric materials, and colossal mag-
netoresistant manganites. The response to external stimuli
is greatly enhanced by the use of competing interactions
in the material. The result are highly complex local struc-
tures. Understanding the local structure on various length
scales is therefore vital to understand these technologically
important as well as scientifically challenging materials.
However, the scope of this paper is to give a practical
138 Th. Proffen, S. J. L. Billinge, T. Egami et al.

overview of the PDF technique and we will focus on a

single problem, understanding the metal-to-insulator (MI)
phase transition in the colossal magnetoresistant (CMR)
manganite La1x Cax MnO3 . A much more comprehensive
overview of this class of exciting new materials can be
found in the book by Egami and Billinge (2002).
La1x Cax MnO3 shows a MI phase transition from insu-
lating paramagnetic phase to a metallic ferromagnetic
phase for compositions from x  0:2 to x 0:5 as the
temperature is decreased. For x 0:25 the transition tem-
perature is Tc  230 K. In the insulating phase charges are
localized, in other words, manganese exists as Mn3 and
Mn4 . In the metallic case, charges are delocalized and
we have Mn3x . We will refer to the two phases as
localized and delocalized phase, respectively. Now the
question is, how does the charge state affect the PDF?
The answer is that charge state and structure are linked
through the Jahn-Teller effect (Billinge et al., 1996; Louca
et al., 1997). If manganese is in the Mn3 state, the MnO6
octahedron is distorted, showing a MnO long bond of
about 2.15
A. The distortion is visible in the PDF and this
way the PDF becomes a local probe for the charge state
of this material.
Neutron powder diffraction data of La0:75 Ca0:25 MnO3
as a function of temperature were collected on the SEPD
diffractometer at the Intense Pulsed Neutron Source
(IPNS). Details about the sample preparation and experi-
ments are given in Billinge et al. (1996). The data were
processed using PDFgetN (Peterson et al., 2000) and the
resulting reduced structure factor FQ QSQ  1 for lar, however in the localized phase the PDF peak will
the measurement at T 20 K is shown in Fig. 9. The cor-
responding PDF, Gr, is shown as filled circles in
Fig. 10. It should be noted that the NN MnO peaks in
the PDF are negative, because the neutron scattering
length for manganese is negative.
The first analysis of these data was to study the PDF
peak height of the PDF peak at r 2:75
A as a function
of temperature (Billinge et al., 1996). This peak corre-
sponds to the OO distances within the MnO6 octahedra
Fig. 9. Normalized reduced structure function FQ QSQ  1
of La0:75 Ca0:25 MnO3 . Measurements were carried out on SEPD dif-
fractometer at IPNS at T 20 K (from Proffen and Billinge, 2002).
Fig. 10. Experimental PDF (*), Gr, of La0:75 Ca0:25 MnO3 and re-
fined PDF (solid line). The difference is plotted below the curves.
The dashed lines correspond to an error of 2s.
and is sensitive to the charge distribution in the sample.
Assuming that the number of OO bonds is constant, the
PDF peak height and PDF peak width are inversely pro-
portional. Thus the PDF peak height gives us the inverse
measure of the width of the OO bond length distribution
in the sample. In the delocalized phase we expect a sharp
or high PDF peak, since all the MnO6 octahedra are regu-
broaden due to contributions of the OO bond lengths of
Mn3 O6 and Mn4 O6 octahedra. The PDF peak heights
for La1x Cax MnO3 with x 0:12, x 0:21 and x 0:25
as function of temperature are shown in Fig. 11. The in-
sets show the resistivity of the samples are function of
temperature. The lowest doped sample (x 0:12) shows
no MI transition and the PDF peak height drops as func-
tion of temperature due to the PDF peaks broaden as the
amplitude of thermal vibrations increases. For the other
two samples a MI transition is observed and the MI transi-
tion temperature, Tc, is indicated by an arrow. The data
clearly show that charges begin to localize, upon heating,
well before the MI transition temperature is reached. In
fact based on X-ray PDF measurements the existence of
nanometer length scale the coexistence of delocalized and
localized phase well within the localized region of the
phase diagram was demonstrated (Billinge et al., 2000b).
The next step of data analysis is to quantify the evolution
of the phase separation as function of temperature. Now,
instead of simply monitoring peak height which is a rela-
tive measure of the phase separation, we fit the data with
models which exemplify the JT and non-JT distorted octa-
hedra and quantify the phase separation on an absolute
scale. To achieve this, full profile PDF refinements were
carried out using the program PDFFIT (Proffen and Bil-
linge, 1999). The initial structural parameters for both
phases were taken from refinements of the undoped mate-
rial, LaMnO3 (Proffen et al., 1999) (localized phase) and
La0:75 Ca0:25 MnO3 at T 20 K (delocalized phase). The
refinement result over a wide r range for the delocalized
phase is shown as solid line in Fig. 10. The difference is
Structural analysis of complex materials 139


a 
a 
b


b

Fig. 12. Refinement results for (a) T 20 K and (b) T 220 K. The
crosses mark the data, the solid line is the calculated PDF. The PDFs
from delocalized and localized phases are shown as dashed and
dotted lines, respectively (from Proffen and Billinge, 2002).


c regular octahedra, which are related to the proportion of
Fig. 11. Normalized height of the PDF peak at r 2.75 A
vs. tem-
perature for various compositions x. (a) x 0:25, (b) x 0:21 and
(c) x 0:12. The insets show the resistivity vs. temperature for the
same samples. The arrows indicate the MI transition temperature in
the insets and the main panel (from Billinge et al., 1996).
localized and delocalized phases in the sample.
The fraction of delocalized phase, fd , is shown in
Fig. 13. It is obtained directly from the two phase refine-
ments described above. Several observations can be made
by inspecting Fig. 13: The first observation is that even at
the lowest temperature, T 20 K, about 10% of the sam-
ple is in the localized phase. This is consistent with find-
ings using PDF analysis based on high energy X-ray dif-
fraction (Billinge et al., 2000b). The second observation is
the onset of charge localization at temperatures below Tc.
This again is consistent with the PDF peak height analysis
discussed above. However, the earlier work did not allow
conclusions about the absolute fractions of localized and

shown below the curves. The two phase refinements were

limited to the low r range between 1:7 < r < 3:2
A. This
range describes mainly the geometry of the MnO6 octa-
hedra. The model consists of a mixture of JT distorted
octahedra and non-JT distorted, regular, octahedra. Since
we are only fitting over a very narrow range in r, and the
cross correlation term has been neglected. The only para-
meters refined are the phase fraction of localized versus
delocalized phase and a scale factor for lattice parameters
and thermal parameters to account for the change in tem-
perature. This gave a very constrained and stable refine-
ment. At this point it is worth pointing out that the pro-
gram PDFFIT is able to carry out refinements using
multiple phases as well as multiple data sets. The program
is controlled by a command language and virtually any
constraint imaginable can be realized. The refinement re- Fig. 13. Temperature dependence of the proportion of MnO6 octahe-
dra that are regular (no JT distortion), fd , as determined from the two-
sults for two selected temperatures, T 20 K and
phase fitting to the PDF (see text for details). The vertical dashed line
T 220 K, are shown in Fig. 12. These refinements al- indicates the temperature of the MI transition (from Proffen and Bill-
lowed one to extract the absolute proportions of JT and inge, 2002).
140
delocalized carriers in the sample. Similarly, the fractions
of localized and delocalized carriers in the sample as a
function of charge concentration was determined from an
x-dependent study in the Sr doped system by integrating
the area under the nearest neighbor peak (Louca et al.,
1997; Louca and Egami, 1999). The last and most surpris-
ing observation from Fig. 13 is the fact that even at room
temperature only about half of the sample has transformed
into the localized phase and half of the sample remains in
the metallic delocalized phase. It is interesting to note that
the fraction of delocalized carriers is about 50% as a func-
tion of charge concentration as well (Louca et al., 1997;
Louca and Egami, 1999). This observation led them to
speculate the percolation mechanism as the origin of the
MI transition (Egami, 1996; Louca et al., 1997). This ob-
servation seems to be confirmed by recent neutron small
angle scattering measurements Radaelli and Argyriou
(2001) which also indicate that 50% of the sample is pre-
sent in form of ferromagnetic clusters or regions of delo-
calized phase at room temperature. Finally, the informa-
tion obtained by the PDF analysis was critical in
elucidating the true origin of the ionic size effect (Hwang
et al., 1995) on the CMR, which is critical in the fun-
damental understanding of the CMR effect (Egami and
Louca, 2002).
Again the study of the local structure as opposed to
knowing the long range average structure has allowed
scientists to take one more step towards understanding the
astonishing properties of CMR materials on an atomic
scale. The presented two phase refinement of the neutron
PDF data demonstrates the current state-of-the-art in full
profile refinement of PDF data.
Crystallographically challenged materials
So far we have presented examples of disordered but still
well behaved crystals showing sharp Bragg peaks. This

a 
Fig. 14. Powder diffraction patterns of hexa-
gonal WS2 and exfoliated restacked WS2 : (a)
raw diffraction intensity data of hexagonal
WS2 ; (b) reduced structure function,
FQ QSQ  1, obtained from (a); (c)
raw intensity data of exfoliated restacked
WS2 ; and (d) reduced structure function,
FQ, obtained from (c) (from Petkov et al.,
2000a).

c 
Th. Proffen, S. J. L. Billinge, T. Egami et al.
allows one to use the tools of conventional crystallography
to determine the average structure of those materials. The
prerequisite for this type of analysis is long-range order.
Glasses and liquids on the other hand only show short-
range order and although they can be studied using the
PDF method, we have excluded them from this review as
stated before. Increasingly, new remarkable materials are
discovered which fall between these two extremes. They
show intermediate-range order and the name nanocrystals
has been coined. These materials show only very sparse
and broad Bragg peaks or none at all due to the very lim-
ited structural coherence. However, the PDF method has
the potential to become the standard tool to characterize
the local as well as intermediate structure of these crys-
tallographically challenged materials as they are called in
Egami and Billinge (2002). A number of structure deter-
minations using the PDF of this class of materials have
been carried out by Petkov and Billinge (2002); Petkov
et al. (2002a, b, c) and we will present the work on WS2
(Petkov et al., 2000a) as an example here.
The material WS2 is made up of covalently bonded
S-W-S layers which stack into the three dimensional
long range ordered structure. The diffraction pattern ta-
ken on a laboratory diffractometer using AgKa radiation
(l 0:55
A) is shown in Fig. 14a. The inset shows the
high Q region enlarged. Solving the structure of this pris-
tine form of WS2 is no problem since many sharp Bragg
reflections are observed. After intercalating lithium be-
tween the layers, the layers are stripped apart and the sam-
ple is in the exfoliated stage. Next the lithium can be re-
moved again and the layers restack. The corresponding
diffraction pattern of the exfoliated restacked WS2 taken at
beamline A2 at the Cornell High Energy Synchrotron
Source (CHESS) is shown in Fig. 14c. It is evident from
the diffraction pattern that the restacked material has un-
dergone a dramatic structural change. The sample has en-
tered the state of nano-crystallinity and standard crystal-
b
d
 Structural analysis of complex materials 141


a

Fig. 16. Neutron powder diffractometer NPDF currently under con-

struction at the Lujan Center at Los Alamos National Laboratory. The
image shows instrument technician Melvin Borrego installing second-
ary flight path shielding in the 119 detector bank.

sufficient since defects often govern the properties of inter-


b est of a material. As a result the interest in total scattering
Fig. 15. Experimental PDF data, Gr, for (a) hexagonal WS2 and (b) which includes Bragg as well as diffuse scattering has in-
exfoliated restacked WS2 . The solid line are the calculated data (from creased over the last few years.
Petkov et al., 2000a). The PDF technique has its roots in the study of liquids
and amorphous materials revealing the local structure on
lography is powerless. In Fig. 14b and d the reduced struc- the length scale of a few nearest neighbors in the material.
ture function FQ QSQ  1 are shown. The data Later the PDF technique found an application in studying
were processed using the program RAD (Petkov, 1989) disordered crystalline materials. The studies of strain in
and the resulting PDFs are shown in Fig. 15 as open cir- semiconductor alloys or the hunt for JT distorted MnO6
cles. Inspection of the PDFs show two remarkable aspects: octahedra in CMR manganites are examples discussed in
For both samples, we observe sharp PDF peaks indicating this paper. A new class of materials is grabbing the atten-
a well defined local structure in both cases. Secondly, the tion of scientists around the world: nano-crystals. Any
first two PDF peaks in pristine WS2 have split into four. structural information of these materials remains hidden to
This shows clearly that the symmetry of the local tungsten routine crystallographic methods, since they show no well
environment has fallen. However, one difference between defined Bragg reflections to analyze. The last example in
the PDF of the two samples is the fact that in the case of this paper demonstrated how the PDF method can be used
exfoliated restacked WS2 the amplitude of the PDF peaks to solve the structure of this type of material. Studies so
decrease as a function of distance r. From this fall-off we far have been carried out using high energy X-ray diffrac-
can estimate the structural coherence to be 20
A. All
this information can be obtained by simply looking at the
PDF. The next step is to refine a structural model. In this
case it was done using PDFFIT and the calculated PDFs
are shown as solid lines in Fig. 15. The modelling of the
pristine WS2 was done as a reference refinement and
yielded the already known structure. However, the PDF
analysis also reveals for the first time the structure of ex-
foliated restacked WS2 . Its structure is made up of layers
of distorted WS6 octahedral units, in contrast to the pris-
tine material consisting of layers of perfect WS6 trigonal
prisms. More details on the resulting structural informa-
tion are given in Petkov et al. (2000a).
Summary
Without a doubt the ability to obtain structural information
on an atomic level has revolutionized our knowledge of
how materials work and as our tools to unravel the struc-
ture on various length scales improve, the revolution still
is in progress. It is also becoming clear that information
obtained from routine structure determination is often not
tion. In order to access intermediate range information,
high resolution powder diffraction data are needed, as we
have seen in Fig. 3. The neutron powder diffractometer
(NPD) at the Lujan center at Los Alamos National La-
boratory is the instrument with the highest resolution in
the US and it is currently being upgraded to eventually
become NPDF (see Fig. 16). Available to users in 2003,
this instrument will be dedicated to high resolution total
scattering studies opening the door to investigating nano-
crystalline materials using neutrons. However, the required
sample amounts might still be a challenge in some cases.
But the future is bright with the disordered materials dif-
fractometer at the SNS on the horizon. At the same time a
dedicated PDF beamline at the APS is currently planned
and together with ongoing efforts in software development
and education, the PDF technique has the potential to be-
come the standard tool to characterize the structure of in-
creasingly more complex materials.
Acknowledgments. We would like to thank Peter Peterson and Valeri
Petkov for their help in preparing this paper. This work was in part
supported by the National Science Foundation through grants DMR-
0075149 and CHE-9903706 and by the U.S. Department of Energy
142
through grants DE-FG02-97ER45651 and DE-FG02-01ER45927.
This work has benefited from the use of the Intense Pulsed Neutron
Source at Argonne National Laboratory, funded by the U.S. Depart-
ment of Energy, BES-Materials Science, under Contract W-31-109-
Eng-38, and from the use of the Los Alamos Neutron Science Center
at the Los Alamos National Laboratory, funded by the US Depart-
ment of Energy under contract W-7405-ENG-36 as well as CHESS,
operated by NSF through grant DMR-9713242.
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