Extinction, polarization and crystal monochromators

A number of theories are examined for their predictions of extinction coefficients at large values of extinction, especially as applied to polarization ratios. Although several theories give the behavior expected on the basis of physical reasoning (a polarization ratio approaching unity), the popular theories of Zachariasen [Acta Cryst. (1967), 23, 558-564] and Becker & Coppens [Acta Cryst. (1964), A30, 129-147, 148-153] do not show the correct asymptotic behavior. Although this shortcoming may be of no consequence in ordinary crystallographic applications, it is misleading in predicting the correct polarization factor to be used in connection with a crystal-monochromated apparatus, where the monochromator is usually adjusted to maximize its extinction. The importance of measuring, rather than estimating, the polarization ratio of a crystal monochromator is therefore reemphasized.