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The Rietveld method

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2014 Phys. Scr. 89 098002

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 | Royal Swedish Academy of Sciences Physica Scripta

Phys. Scr. 89 (2014) 098002 (6pp) doi:10.1088/0031-8949/89/9/098002

Invited Comment

The Rietveld method

Hugo M Rietveld
E-mail: [email protected]

Received 22 May 2014

Accepted for publication 9 June 2014
Published 1 August 2014

Abstract
A summary is given of the development of an improved method to handle powder diffraction
data. The resulting method, now called the Rietveld method, uses powder diffraction step-
scanned intensities instead of integrated powder intensities. This enables the full use of the
information content of a powder diagram. The method has revitalized the use of powder
diffraction in structure determination. An unexpected and later development is the use of the
method in quantitative phase analysis. This is now an essential tool in many industrial processes.

Keywords: Rietveld method, powder diffraction, crystallopgraphic computing

(Some figures may appear in colour only in the online journal)

In 1957, I enrolled at the University of Western Australia as a the spacegroup and the unit-cell dimensions. In contrast,
physics student, together with Brian O’Connor and Syd Hall, single-crystal diffraction produces well-resolved intensities.
both of whom became well known crystallographers At that time, the physics department installed the first
(figure 1). I did my PhD study under the supervision of Ted electronic computer, the IBM 1620. Programming was done
Maslen, who had come from Oxford where he had studied in Fortran II, with punched cards for input and output.
under Dorothy Hodgkin. Compared to today’s standards, this computer was a thousand
In 1960, Ted Maslen and I undertook the first single times smaller and slower than any home computer! Never-
crystal neutron diffraction study in Australia on the com- theless, we learned to appreciate the calculating power of this
pound p-diphenyl benzene (figure 2). Automation, particu- new computer.
larly by means of a computer, was hardly known. At the After obtaining my PhD degree in 1964 ([2]) with Dor-
Atomic Research Establishment in Lucas Heights (figure 3), othy Hodgkin (figure 4; who received the Nobel Prize for her
we had to set the crystal orientation on the goniometer head study on penicillin at that time), as my examiner, I joined the
neutron diffraction group of the Reactor Centrum Nederland
by hand. The only automatic process was the theta–2theta
(now Netherlands Energy Research Foundation ECN) in the
scan, producing, in one hour, a piece of paper with approxi-
Netherlands (figure 5). This group had only just been estab-
mately forty intensities per reflection. Because of this, our
lished and was principally engaged in the construction of a
continual attendance was required and we often worked
neutron powder diffractometer. The emphasis here was
twelve-hour shifts. This was hard work. I hoped that the rest
mainly on powder diffraction techniques, because it was
of my scientific career would consist of more intellectual apparent that no large single crystals could be grown of the
activities! Nevertheless all of this was forgotten when, for the materials that were then of interest. The first crystal structures
first time, on a hand-plotted Fourier map, we saw the peaks of to be determined were rather simple and of a high symmetry,
the hydrogen atoms next to the carbon atoms [1]. A moment with the result that the peaks were well resolved and could
to be remembered! It may well be that these early experiences easily be obtained for further refinement. However, with more
led me to vigorously embrace the possibilities of automation complex compounds and those of lower symmetry, the
created by the introduction of computers. They also con- overlap of peaks became so severe that separating them
vinced me at that time that decent crystallographic work could became practically impossible. In an effort to overcome this
only be done by means of single-crystal diffraction. A Guinier problem, the resolution of the diffractometer was significantly
film of the same compound may have consisted of numerous increased by using a wavelength of 2.6 Å and by eliminating
lines, often overlapping, and could only be used to determine the higher order wavelength with a filter of pyrolytic graphite.

0031-8949/14/098002+06$33.00 1 © 2014 The Royal Swedish Academy of Sciences Printed in the UK

Phys. Scr. 89 (2014) 098002 H M Rietveld

Figure 1. Staff and PhD students of the University of Western

Figure 4. With Dorothy Hodgkin at her cottage.
Australia in 1979.

Figure 2. A Fourier map of p-diphenyl benzene.

Figure 5. The HFR reactor at Petten, The Netherlands.

completely resolved. The solution then was to refine the

structure by using not only single Bragg reflection intensities
as data, but also groups of overlapping intensities [3]. This
worked well, but the fact remained that all extra information
contained in the profile of these overlapping peaks was lost.
The next step was to separate the overlapping peaks by trying
to fit Gaussian peaks using least-squares procedures. This
method also had its limitations, however, and did not work for
severe overlaps.
Before the advent of computers, data reduction was a
must in crystallography in order to be able to handle a rela-
tively complex structure. Integrated intensities were therefore
Figure 3. The HIFAR reactor in Lucas Heights, NSW, Australia. the smallest data elements one could work with practically.
To consider using the individual intensities, y i , constituting a
This proved to be of appreciable value, especially for step-canned diffraction diagram as data, was completely
structure determination. For structure refinement, however, unrealistic. With my experience of using computers for sin-
the increase of resolution certainly resulted in a better defined gle-crystal structure refinements and having seen their enor-
pattern, but often not to such an extent that the peaks were mous capacity for handling large amounts of data, I saw that

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Phys. Scr. 89 (2014) 098002 H M Rietveld

Figure 6. Laboratory notebook, 1966.

Figure 7. Neutron Powder diagram of WO(3).

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Phys. Scr. 89 (2014) 098002 H M Rietveld

Figure 8. The number of publications per year citing the Rietveld

Method according to Google Scholar. Figure 9. With Ray Young (left).

Figure 10. The International Workshop on the Rietveld method in Petten, The Netherlands 1989 (ECN).

the spectre of increasing the number of data by a factor of ten

by using the individual intensities y i , instead of the integrated
intensities, constituted no reaI barrier (figure 6). In the first
refinement program, the intensities y i were corrected for
background and were read in together with the value of the
relative contributions each constituent peak made, i.e. the
value of ωik in the expression yobs i
= c′∑k ωik Fk2 + bi [4],
where Fk is the structure factor and bi the background. These
values were calculated from the unit-cell dimensions, the
wavelength and the zeropoint and halfwidth values measured
directly from the diagram. Also, for resolved peaks, the
integrated values were used rather than the y i intensities,
because the Gaussian peak shape did not fit well at lower Figure 11. The number of publications per year citing Rietveld
angles (figure 7). Later, a correction for this asymmetry was quantitative phase analysis according to Google Scholar.
introduced. The non-refinement of the reflection-profile
parameters can be explained by the fact that the then-available
computer, the Electrologica X1, was not powerful enough to method was published [5] that reactions came. At this time, the
solve a least-squares problem of more than a very limited method was mainly used to refine structures from data obtained
number of parameters. With the arrival of the larger Elec- by fixed wavelength neutron diffraction; a total of 172 struc-
trologica X8 computer, the program was rewritten to include tures were refined in this way before 1977. In the previously
the capability of refining the structure as well as profile mentioned paper [5], it had been suggested that the method
parameters [5]. Twenty-seven copies of this program, written could also be applied to x-ray data, but it was not until 1977
in Algol and later, in 1972, in FORTRAN IV, were dis- that the method became generally accepted for x-ray as weIl as
tributed to institutes all over the world. neutron powder diffraction, first with a fixed wavelength and
The method was first reported at the Seventh Congress of then also with a fixed angle (energy dispersive data). This is
IUCr in Moscow in 1966. The response was slight, or, rather, reflected in an increasing number of citations to the original
non-existent, and it was not until the full implementation of the papers ([4] and [5]) as shown in Google Scholar (figure 8).

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Phys. Scr. 89 (2014) 098002 H M Rietveld

Figure 12. A Rietveld quantitative phase analysis diagram (Panalytical).

Figure 13. King Gustav of Sweden presents the Aminoff Prize

in 1995.

While I named my method originally the Profile

Refinement Method, many authors used different names in
the literature. In order to prevent further confusion, during the Figure 14. The Aminoff Certificate, 1995.

Neutron Conference in Cracow, Terry Sabine and Ray Young

(figure 9) proposed to name the method the Rietveld Method,
and this was then accepted by the Commission on Neutron An unexpected application of the method was to quan-
Diffraction. titative phase analysis. This resulted in an increased use in
In June 1989, the IUCr Commission on Powder Dif-
industry (figure 11) and also to the marketing of commercial
fraction in co-operation with the Netherlands Energy
software by firms such as Panalytical (figure 12), Bruker and
Research Centre (ECN) organized a workshop on the Rietveld
Rikagu.
Method in Petten, the Netherlands (figure 10). This resulted in To see how the method has developed is to me most
the publication of the IUCr Monograph The Rietveld Method, gratifying and I am grateful to have been able to contribute to
edited by R A Young. the importance of the field of crystallography.

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Phys. Scr. 89 (2014) 098002 H M Rietveld

For my method I received the following awards: References

• Aminoff Prize by the Royal Academy of Sciences (1995)
(figures 13 and 14). [1] Clews C J B, Maslen E N, Rietveld H M and Sabine T M 1961
Nature 192 154
• Barrett Award by the Denver x-ray Conference (2003).
[2] Rietveld H M 1963 PhD Thesis Univ. of Western Australia
• Award for Distinguished Powder Diffractionist by the [3] Rietveld H M 1966 Acta Cryst. 20 508
European. [4] Rietveld H M 1967 Acta Cryst. 22 151
• Powder Diffraction Conference (2010). [5] Rietveld H M 1969 J. Appl. Cryst. 2 65
• Hans-Kühl-Medaille by Die Gesellschaft Deutscher
Chemiker (2010).