Rietveld refinement

1. Scale factor.
In Rietveld refinement, the scale factor is a parameter used to account for any systematic errors or
uncertainties in the intensity measurements of the diffraction data. The scale factor is applied to the
calculated diffraction pattern to ensure that it matches the observed diffraction pattern. The scale factor
is typically included as a refinement parameter in the Rietveld refinement process. It is usually
expressed as a fractional value, with a value of 1.0 indicating that the calculated diffraction pattern
matches the observed pattern perfectly.
2. Scale factor, zero point of detector, 1st background parameter and lattice constants.
• Zero point of the detector refers to the correction for any systematic shift or offset in the position
of the diffraction peaks recorded by the detector. The zero-point correction considers any
instrumental factors or misalignments that may cause a shift in the recorded positions of the
diffraction peaks. These factors can include errors in the calibration of the detector or sample
displacement.
• The background parameter refers to the parameter that accounts for the background scattering
in the diffraction pattern. The background scattering arises from various sources such as
incoherent scattering, fluorescence, and sample impurities.
In case of very sloppy background, it may be wise to actually refine at least two background
parameters, or better fix the background using linear interpolation between a set of fixed points
provided by user.
3. Add the refinement of atomic positions and (eventually) an overall Debye-Waller factor,
especially for high temperature data.
• The Debye-Waller factor, also known as the thermal factor or atomic displacement factor, is a
parameter used in crystallography to account for the thermal motion or disorder of atoms in a
crystal lattice. It quantifies the extent of atomic vibrations around their average positions. The
Debye-Waller factor is denoted by the symbol B or U and is typically expressed in units of
Ångstroms squared (Å^2) or in reciprocal units (Å^-2). It is related to the mean-square atomic
displacement of the atoms in the crystal.
4. Add the peak shape and asymmetry parameters.
Peak shape parameters: Peak shape parameters are used to model the intrinsic shape of
diffraction peaks. These parameters describe the peak width and profile in terms of instrumental
broadening, crystallite size, and strain effects. Common peak shape functions used include
Gaussian, Lorentzian, pseudo-Voigt, or split pseudo-Voigt functions. During the refinement
 process, the peak shape parameters are adjusted to minimize the difference between the
observed and calculated diffraction patterns. By optimizing these parameters, the peak widths
and profiles in the calculated diffraction pattern are adjusted to match those observed
experimentally.
Asymmetry parameters: Asymmetry parameters account for any asymmetry or distortion in the
shape of the diffraction peaks. These parameters are particularly relevant for peaks affected by
preferred orientation, microstrain, or other crystallographic distortions. Asymmetry parameters
can be described using various mathematical functions or empirical expressions, depending on
the nature of the asymmetry observed. They are adjusted during the refinement process to
improve the fit between the observed and calculated diffraction patterns. Optimizing the
asymmetry parameters helps to accurately model and reproduce any observed asymmetry or
distortion in the diffraction peaks.
5. Add atom occupancies (if required)!
6. Turn the overall temperature factor into individual isotropic thermal parameters.
7. Include additional background parameters (if background is refined))
8. Refine the individual anisotropic thermal parameters if the quality of the data is good enough.
9. In case of constant wavelength data, the parameters Sycos and/or Sysin to correct for
instrumental or physical aberrations with a COS or SIN angular dependence.
• Sycos: The "Sycos" parameter corrects for systematic errors or aberrations that have a cosine
angular dependence. These aberrations can arise from factors such as sample displacement,
sample transparency, or axial divergence in the diffractometer setup. The Sycos parameter is
usually associated with the cosine component of the angular dependence and is used to adjust
the intensity of the diffraction peaks accordingly.
• Sysin: The "Sysin" parameter corrects for systematic errors or aberrations that have a sine
angular dependence. These aberrations can occur due to factors such as zero-point errors in the
diffractometer, sample surface roughness, or axial divergence in the diffractometer setup. The
Sysin parameter is associated with the sine component of the angular dependence and is used
to adjust the intensity of the diffraction peaks accordingly.
10. Microstructural parameters: size and strain effects.