Lattice parameter measurement using Le Bail versus structural Rietveld

refinement: A caution for complex, low symmetry systems

V. K. Petersona
University of Technology, Sydney, Australia

Received 23 February 2004; accepted 1 September 2004

The measurement of lattice parameters using the Le Bail method was shown to be inappropriate for
a complex, low symmetry, structure, even with high resolution synchrotron diffraction data. The
method failed as a result of ambiguous indexing in the absence of constraints on diffraction
intensities, that arise when a structural model is used, combined with the large number of reflections.
A caution for the use of the Le Bail and other whole-powder pattern decomposition methods is
presented, particularly for high reflection density data. 2005 International Centre for Diffraction
Data. DOI: 10.1154/1.1810156
Key words: Rietveld, Le Bail, X-ray powder diffraction

I. INTRODUCTION

Full pattern methods for the determination of unit-cell

parameters from polycrystalline diffraction data can be divided into two categories. One category involves the computation of reflection intensities from a structural model, often
referred to as the Rietveld method Rietveld, 1969. The
other category is referred to as whole-powder pattern decomposition methods, in which the reflection positions are also
determined from the space group and initial unit cell parameters, however, the reflection intensities are treated as arbitrary unknowns Pawley, 1981; Toraya, 1986; Le Bail et al.,
1988. The Le Bail method Le Bail et al., 1988 is a popular
method for whole pattern decomposition, where reflection
intensity values are initially set to arbitrary values. The intensities evolve iteratively, where reflection intensity values
are arbitrarily assigned to estimates obtained by apportioning
data values amongst the contributing reflections. Other parameters including background function, unit cell, and peak
profile parameters can be refined simultaneously with the Le
Bail intensity extraction. Le Bail fitting is considered as standard functionality in modern Rietveld software http://
www.ccp14.ac.uk/solution/lebail/#software. In comparison
the older Pawley method treats reflection intensities as leastsquares parameters Pawley, 1981; Toraya, 1986.
The Le Bail and other pattern decomposition methods
are often the only way to apply full pattern methods when
structures are not known or are difficult to describe, such as
with disordered structures. These methods may also be used
preferentially to the Rietveld method when experimental artifacts are difficult to model, as may be the case when in situ
diffraction cells are used Walker et al., 2002. These techniques are also being increasingly used to obtain reflection
intensity estimates as a precursor to structure solution Morris et al., 1992; Le Bail and Fourquet, 1992.
Despite the advantages and popularity of the Le Bail
method, there exist surprisingly few publications concerned
with the technique Le Bail, 2002, and none concerning how
the method can produce misleading results. While in many
cases the Le Bail technique produces quite good results, this
publication presents a case where the Le Bail results are
a

Electronic mail: vanessa.peterson@nist.gov

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Powder Diffraction 20 1, March 2005

shown to be invalid, as a likely consequence of the combination of the large unit cell and low symmetry of the system
being studied. Recommendations on how to avoid this are
also presented.

II. EXPERIMENTAL
A. Tricalcium silicate sample

A phase pure C3S type T1 tricalcium silicate sample was

obtained from Construction Technology Laboratories CTL
Inc., Illinois. Previous X-ray Fluorescence XRF analyses
Peterson et al., 2004 had shown the tricalcium silicate powder sample to contain no elemental impurities at a level expected to contribute to any stabilisation of high temperature
polymorphs or significant effects on the crystal chemistry.

B. Synchrotron X-ray powder diffraction data

collection

Synchrotron X-ray powder diffraction data were gathered using the powder diffractometer on beamline X7A at the
National Synchrotron Light Source NSLS at Brookhaven
National Laboratories BNL in Upton, NY. The tricalcium
silicate powder sample was inserted into a 0.2 mm quartz
type capillary amorphous SiO2 and the end sealed. The
sample was rotated in the furnace during data acquisition.
The wavelength used was determined as 0.703213 using
the National Institute of Standards and Technology NIST,
Gaithersburg, MD CeO2 674 standard. Data acquisition
lasted approximately 1 h per pattern. The X-ray beam incident to the sample was 2.0 by 0.8 mm. A Kr position sensitive detector was used and data were collected over the 2
range 250, with a step size of 0.01. The temperature
range chosen was ambient to 740 C, the range expected to
correspond with the structural transition between the tricalcium silicate triclinic type T1 and triclinic type T2. Patterns
were recorded at 20 C intervals during heating and cooling
over the temperature range, and the temperature was held
constant during the collection of each pattern. The furnace
temperature was calibrated separately from the experimental
run using the known thermal expansion of NaCl.

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2005 JCPDS-ICDD

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Figure 1. Rietveld top and Le Bail bottom refinement plots for T1 tricalcium silicate data at ambient temperature. Insets feature regions of the data
for specific fingerprint regions used to identify the polymorphs of tricalcium
silicate from diffraction data Taylor, 1997; Bigar et al., 1967.

C. Le Bail and Rietveld refinements

Rietveld refinements and Le Bail fits were performed

using the same refinement program, RIETICA Hunter, 1998.
Peak profiles were modelled using a pseudo-Voigt peak
shape Thompson et al., 1987 with the FCJ asymmetry
function Finger et al., 1994. A 24-term Chebyshev type I
background function was used, which helped model the contribution to the pattern background from the amorphous SiO2
capillary used, visible in the pattern as a hump underneath
the lower angle reflections. Other experimental parameters
refined were the instrument zero, scale factor, the lattice parameters, and the peak shape parameters u , v , w , 0, and 1.
For Rietveld fits, the T1 triclinic tricalcium silicate structure
of Golovastikov et al. 1975 was used, and both atomic
positions and atomic displacement parameters grouped by
atom type were refined. Excluding the background, the total
number of refined parameters was 324 in the Rietveld refinements, and 13 for the Le Bail refinements.

III. RESULTS AND DISCUSSION

Le Bail fitting was initially performed, using the data for

both heating and cooling over the temperature range, because
of the capability of the method for the fast observation of
lattice dynamics. Excellent agreement between the model
and the data was obtained for all data sets, as shown in
Figures 1 and 2, and in Table I. Despite this, the resulting
lattice parameters were internally inconsistent, as shown in
Figures 3 and 4. Subsequently, Rietveld fitting was performed with the model of Golovastikov et al. 1975 of T1
triclinic tricalcium silicate. Despite the inadequacy of this
model, which does not account for many small superstructure reflections arising from structural modulation Peterson
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Powder Diffr., Vol. 20, No. 1, March 2005

Figure 2. Rietveld top and Le Bail bottom refinement plots for T1 tricalcium silicate at ambient temperature detailing the fine structure fit.

et al., 2004; Urabe et al., 2000; Peterson, 2003, the lattice

parameters obtained from the Rietveld fits are internally consistent, and differ significantly from the Le Bail fits, as
shown in Figures 35. The fact that the Le Bail and fullstructural Rietveld derived results do not match in any singular case indicates that at least one of them is incorrect. The
agreement factors for the Rietveld fits are not as good as
those obtained from the Le Bail fit Table I. Inspection of
the refinement plots for the fine structure detail Figure 2
also indicated a better fit to the data by the Le Bail model.
Inspection of the whole pattern fit of the Le Bail model to the
data, particularly for some of the larger reflections Figure
1, indicated a better fit by the Rietveld model.
From these results it is concluded that the Le Bail lattice
parameters are inaccurate, and that despite the inadequacies
of the Golovastikov et al. T1 structural model, these results
are preferable to the Le Bail fit. It is interesting to note that
for any singular Le Bail refinement case the obtained cell
constants were within acceptable limits, based on the determined structure of Golovastikov et al., and if it were not for
the erratic trends observed Figures 3 and 4, these results
may never have been questioned as incorrect.
The reasons for the failure of the Le Bail method on
these data sets is clear in retrospect. Despite the very high

TABLE I. Error indices for representative Le Bail and Rietveld refinements

during the heating of tricalcium silicate.
Temp
C

Le Bail
X2

Le Bail
Rp

Rietveld
X2

Rietveld
Rp

Ambient
54921
68327
74031

16.46
3.78
3.95
3.64

2.34
2.04
2.05
2.16

22.81
7.47
6.96
5.55

3.52
3.29
2.99
3.01

Lattice parameter measurement using Le Bail versus structural ...

15

Figure 3. Cell lengths for tricalcium

silicate during heating and cooling using the Rietveld method left and the
Le Bail method right.

resolution data sets, the very large density of reflections

present at all diffraction angles enables the Le Bail method to
fit multiple sets of lattice parameters to the diffraction data,
as reflection intensities are arbitrary. In contrast, Rietveld
fitting sets diffraction intensities according to the structural
model, so the fit is constrained to keep intense reflections
aligned with strong peaks in the data. It should be acknowledged that this case represents a low-symmetry structure
with many reflections. Another case of the Le Bail method
producing different lattice parameters than those calculated
from the Rietveld method has, however, been noted for a
high symmetry I4 / mmmK2NiF4 structure, using constantwavelength neutron data Mehta, 2003.

IV. CONCLUSION

The observation of lattice parameters using the Le Bail

method was shown inappropriate for a complex, low symmetry, structure, even with very high quality high resolution
synchrotron diffraction data. The method fails due to the absence of the constraints on the diffraction intensities that will
arise from the use of a structural model, as there are multiple
ways that the pattern can be indexed as a consequence of the
large number of reflections spanning the entire data range.
While no attempt was made to repeat the fitting using the
Pawley technique, this method could also be expected produce the same problem, as again the reflection intensities are

Figure 4. Cell angles for tricalcium

silicate during heating and cooling using the Rietveld method left and the
Le Bail method right.

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Powder Diffr., Vol. 20, No. 1, March 2005

V. K. Peterson

16

Figure 5. Cell volume for tricalcium silicate during heating and cooling calculated using the Rietveld method left and Le Bail method right.

arbitrary. While whole-powder pattern decomposition methods are inarguably of great value and excellent tools, care
must be taken to assure that a pattern is uniquely indexed,
and where possible, Le Bail results should be compared with
results from even an imperfect structural model.

ACKNOWLEDGMENTS

The experimental section of this work was completed as

part of investigations for a Ph.D. supported by Australian
Ph.D. and Australian Institute of Nuclear Science and Engineering Post-Graduate Research Awards. Support from the
Australian Nuclear Science and Technology Organisation
ANSTO and Australias Access to Major Research Facilities Program is recognized. Additional support for this publication provided by the University of Technology, Sydney,
Australia. The author is grateful to Dr Brian H. Toby from
the NIST Center for Neutron Research for reviewing the
manuscript.
Bigar, M., Guinier, A., Mazires, C., Regourd, M., Yannaquis, N., Eysel,
W., Hahn, T., and Woermann, E. 1967. Polymorphism of tricalcium
silicate and its solid solutions, J. Am. Ceram. Soc. 50, 609619.
Finger, L. W., Cox, D. E., and Jephcoat, A. P. 1994. A correction for
powder diffraction peak asymmetry due to diaxial divergence, J. Appl.
Crystallogr. 27, 892900.
Golovastikov, N. I., Matveera, R. G., and Belov, N. V. 1975. Crystal
structure of tricalcium silicate 3CaO. SiO2 = C3S, Sov. Phys. Crystallogr. 20, 721729.
http://www.ccp14.ac.uk/solution/lebail/#software
Hunter, B. 1998. Rietica - A visual Rietveld program, Int. Union Crystallogr. Com. On Powder Diffraction Newsletter 20.
Le Bail, A. 2002. Le Bail method full saga, http://sdpd.univ-lemans.fr/
iniref/lbm-story/

17

Powder Diffr., Vol. 20, No. 1, March 2005

Le Bail, A., Duroy, H., and Fourquet, J. L. 1988. Ab-initio structure

determination of LiSbWO6 by X Ray powder diffraction, Mater. Res.
Bull. 23, 447452.
Le Bail, A. and Fourquet J. L., 1992. Crystal structure and thermal behaviour of H2Ti3O7: A new defective ramsdellite form from Li+ / H+
exchange on Li2Ti3O7, Mater. Res. Bull. 27, 7585.
Mehta, A. 2003. Personal communication.
Morris, R. E., Harrison, W. T. A., Nicol, J. M., Wilkinson, A. P., and
Cheetham, A. K. 1992. Determination of complex structures by combined neutron and synchrotron X-ray powder diffraction, Nature London 359, 519522.
Pawley, G. S. 1981. Unit-cell refinement from powder diffraction scans,
J. Appl. Crystallogr. 14, 357361.
Peterson, V. K. 2003. Ph.D. Thesis:, Powder diffraction investigations of
cement and its major component, tricalcium silicate, University of
Technology, Sydney, Australia.
Peterson, V. K., Hunter, B., and Ray, A. 2004. Tricalcium silicate T1 and
T2 polymorphic investigations: Rietveld refinement at various temperatures using synchrotron powder diffraction, J. Am. Ceram. Soc. 879,
16251634.
Rietveld, H. M. 1969. A profile refinement method for nuclear and magnetic structures, J. Appl. Crystallogr. 2, 6571.
Taylor, H. F. W. 1997. Cement Chemistry, Telford, London.
Thompson, P., Cox, D. E., and Hasting, J. B. 1987. Rietveld refinement of
Debye-Scherrer synchrotron X-ray data from Al2O3, J. Appl. Crystallogr. 20, 7983.
Toraya, H. 1986. Whole-powder-pattern fitting without reference to a
structural model: Application to X-ray powder diffraction data, J. Appl.
Crystallogr. 19, 440447.
Urabe, K., Shirakami, T., and Iwashima, M. 2000. Superstructure in a
triclinic phase of tricalcium silicate, J. Am. Ceram. Soc. 83, 1253
1258.
Walker, D., Clark, S. M., Cranswick, L. M. D., Johnson, M. C., and Jones,
R. L. 2002. O2 volumes at high pressure from KCLO4 decomposition:
D as a siderophile element pump instead of a lid on the core,
Geochem. Geophys. Geosys. 3, 15252027.

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