Rietveld refinement round robin. I. Analysis of standard X-ray and neutron data for PbSO4

Abstract

The Commission on Powder Diffraction of the International Union of Crystallography has undertaken an intercomparison of Rietveld refinements performed with two `standard' PbSO4 powder diffraction patterns: a conventional (two-wavelength) X-ray pattern collected on a Bragg–Brentano diffractometer with Cu Kα radiation and a constant-wavelength neutron pattern collected on the D1A diffractometer at the Institut Laue–Langevin. The aims of this project were: (i) to evaluate a cross section of currently used Rietveld refinement software; (ii) to examine the range and effect of various strategies of Rietveld refinement; (iii) to assess the precision and accuracy (spread) of the parameters derived by Rietveld analysis. 23 participants provided 18 refinements with the X-ray data and 20 refinements with the neutron data, using 11 different Rietveld-analysis programs. Analysis of the submitted results shows that refinement strategies play a large part in determining the detailed outcome of a Rietveld refinement. The wide variation in the values of the agreement indices obtained in these studies of the same data sets highlights the need for standardization both of the refinement procedures and of the type of data included in the algorithms used for assessing the fit. The major factors limiting the accuracy of the derived PbSO4 crystal structure parameters were: (i) use of insufficiently flexible peak shape and/or background functions; (ii) elimination of the high-angle diffraction data from the refinement; (iii) inclusion of an insufficiently wide range of diffraction angles on either side of the centroid of each peak during the step intensity calculation; and, additionally for X-rays, (iv) simultaneous release of the O-atom site-occupancy and displacement parameters. Rietveld analysis of the PbSO4 X-ray powder diffraction data provided atomic coordinates and isotropic displacement parameters for the Pb and S atoms that are precise (i.e. have small e.s.d.s) and are in reasonable agreement with the values derived from a single crystal study (viz the spread of coordinates is over the range 0.007–0.042 Å). On the other hand, the `light' O-atom parameters show relatively poor precision and have a disconcertingly wide spread of values about the weighted mean (viz 0.12–0.19 Å for the coordinates). Despite the much lower intrinsic resolution of the neutron data (i.e. peak widths some four times those of the X-ray data), the coordinates and anisotropic displacement parameters obtained for the Pb and O atoms are very precise and have a relatively narrow distribution about the single-crystal results, namely 0.004–0.020 Å for the coordinates. The range of coordinates determined from the neutron data for the relatively `light' S atom is correspondingly larger, namely 0.024–0.043 Å, about equivalent to that obtained from the X-ray data. In general, and as expected, the e.s.d.s from the Rietveld analyses are substantially smaller than the observed inter-refinement variation of the unit-cell dimensions, atomic coordinates and isotropic displacement parameters by factors of up to, respectively, 17, 5 and 22 for X-rays, and 25, 3 and 5 for neutrons. This investigation indicates that results of possibly high precision but low accuracy are not uncommon in Rietveld analysis. The disparity between individual refinements can be expected to increase further when, unlike here, the analyses are undertaken using data sets collected under diverse experimental conditions.