Data Collection Strategies for Constant Wavelength Rietveld Analysis

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Abstract
In the Rietveld method for the analysis of powder diffraction data the entire pattern is calculated using a model for the positions of the peaks (the unit cell parameters), their intensities (dependent on the atomic positional and thermal parameters, preferred orientation, etc.) and their widths and shapes, together with a description of the background. The calculated pattern is then compared with the observed step profile, point by point, and the model parameters are adjusted by least-squares methods.In order to ensure the best possible outcome of the refinement, a number of critical decisions must be made prior to the collection of the step intensities. For constant wavelength diffractometers, these decisions relate to the wavelength, beam collimation, range of diffraction angles, angular distance between steps, and counting time (X-rays) or monitor setting (neutrons) at each step. The effect of the first three of these factors is well known, but the selection of appropriate values for the counting time T (in effect, the intensity) and for the step interval (which, for a given scan range, determines the number of steps, N) is not straightforward. In fact, N and T are usually chosen more by tradition or by pressure of instrument time than by a consideration of their possible effect on the results of the analysis.Since each measured step intensity is used in the Rietveld method, the number of ‘observations’, N, in a scan can be made arbitrarily large (independent of the number of Bragg reflections) by decreasing the step interval. It is, however, the intensities of the Bragg peaks that are the fundamental quantities in any structure analysis, not the step intensities themselves. Thus, although the precision of the peak intensity measurement is improved by increasing N or T, this only occurs up to the point where counting variance becomes negligible in relation to other sources of error; further increases provide no additional structural information.Systematic studies of the effect of variations in T indicate that the optimum value of the maximum step intensity is only a few thousand counts. If significantly larger numbers of counts are accumulated, the accuracy of the structural parameters is not improved, time is wasted, and the usual weighting scheme based on counting variance becomes inappropriate (i.e., the parameter esd's reflect their precision rather than their accuracy). In the case of step width, the optimum value is between one-fifth and one-half the minimum full-width at half-maximum (FWHM) of well-resolved peaks, the exact value depending on T and the complexity of the diffraction pattern. Smaller steps provide little or no improvement in parameter accuracy (especially when step intensities are large) and, at the same time, introduce serial correlation between adjacent residuals in the profile, again leading to wasted time and corruption of the esd's.In practice, it is the combination of N and T chosen for the experiment that is of greatest importance in determining the efficiency of the data collection strategy. If the pattern has many overlapping peaks, N should be large, corresponding to a step interval of about FWHM/5, to provide adequate peak resolution, and T should be correspondingly small to minimize serial correlation. For a fixed total data collection time, a given level of Rietveld precision can be achieved more efficiently by the use of large N and small T than by combinations of small N and large T. The implications of these restrictions for ‘real-time’ data collection are noteworthy.