Optical rotatory dispersion

Optical rotatory dispersion is the variation in the optical rotation of a substance with a change in the wavelength of light. Optical rotatory dispersion can be used to find the absolute configuration of metal complexes. For example, when plane-polarized white light from an overhead projector is passed through a cylinder of sucrose solution, a spiral rainbow is observed perpendicular to the cylinder. When white light passes through a polarizer, the extent of rotation of light depends on its wavelength. Short wavelengths are rotated more than longer wavelengths, per unit of distance. Because the wavelength of light determines its color, the variation of color with distance through the tube is observed. This dependence of specific rotation on wavelength is called optical rotatory dispersion. In all materials the rotation varies with wavelength. The variation is caused by two quite different phenomena. The first accounts in most cases for the majority of the variation in rotation and should not strictly be termed rotatory dispersion. It depends on the fact that optical activity is actually circular birefringence. In other words, a substance which is optically active transmits right circularly polarized light with a different velocity from left circularly polarized light. In addition to this pseudodispersion which depends on the material thickness, there is a true rotatory dispersion which depends on the variation with wavelength of the indices of refraction for right and left circularly polarized light. For wavelengths that are absorbed by the optically active sample, the two circularly polarized components will be absorbed to differing extents. This unequal absorption is known as circular dichroism. Circular dichroism causes incident linearly polarized light to become elliptically polarized. The two phenomena are closely related, just as are ordinary absorption and dispersion. If the entire optical rotatory dispersion spectrum is known, the circular dichroism spectrum can be calculated, and vice versa.