Abstract
Summary The rotation of the plane of linearly polarized light by an optically-active medium arises from a difference between the refractive indices of the medium for left- and right-circularly polarized light. The circular birefringence is related to a circular dichroism, which is exhibited by all molecules which are not superposable on their mirror image and exist as laevo- and dextro-rotatory isomers. The circular dichroism of a dissymmetric molecule in a particular absorption region originates from an electronic transition with collinear electric and magnetic dipole moments, corresponding to the displacement of a molecular valency electron through a helical path by the absorption of radiation. The right- or left-handed form of the helical path depends upon the molecular structure, and the absolute stereochemical configuration of dissymmetric molecules may be determined by comparing their circular dichroism spectra with the calculated rotational strengths. In addition the polarization direction of an electric moment and the magnitude of a magnetic moment of an electronic transition in a dissymmetric molecule may be derived from circular dichroism measurements.
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