The number of reflection intensities measured in a crystallographic experiment is large, and commonly exceeds the number of parameters to be determined. It was first realized by Hughes (1941) that such an overdetermination is ideally suited for the application of the least-squares methods of Gauss (see, e.g., Whittaker and Robinson 1967), in which an error function S, defined as the sum of the squares of discrepancies between observation and calculation, is minimized by adjustment of the parameters of the observational equations. As least-squares methods are computationally convenient, they have largely replaced Fourier techniques in crystal structure refinement. In addition to the positional and thermal parameters of the atoms, least-squares procedures are used to determine the scale of the data, and parameters such as mosaic spread or particle size, which influence the intensities through multiple-beam effects (Becker and Coppens 1974a, b, 1975). It is not an exaggeration to say that modern crystallography is, to a large extent, made possible by the use of least-squares methods. Similarly, least-squares techniques play a central role in the charge density analysis with the scattering formalisms described in the previous chapter. The following description follows closely the treatment given by Hamilton (1964).