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Concept
Magnetic circular dichroism
Résumé
Magnetic circular dichroism (MCD) is the differential absorption of left and right circularly polarized (LCP and RCP) light, induced in a sample by a strong magnetic field oriented parallel to the direction of light propagation. MCD measurements can detect transitions which are too weak to be seen in conventional optical absorption spectra, and it can be used to distinguish between overlapping transitions. Paramagnetic systems are common analytes, as their near-degenerate magnetic sublevels provide strong MCD intensity that varies with both field strength and sample temperature. The MCD signal also provides insight into the symmetry of the electronic levels of the studied systems, such as metal ion sites.
It was first shown by Faraday that optical activity (the Faraday effect) could be induced in matter by a longitudinal magnetic field (a field in the direction of light propagation). The development of MCD really began in the 1930s when a quantum mechanical theory of MOR (magnetic optical rotatory dispersion) in regions outside absorption bands was formulated. The expansion of the theory to include MCD and MOR effects in the region of absorptions, which were referred to as “anomalous dispersions” was developed soon thereafter. There was, however, little effort made to refine MCD as a modern spectroscopic technique until the early 1960s. Since that time there have been numerous studies of MCD spectra for a very large variety of samples, including stable molecules in solutions, in isotropic solids, and in the gas phase, as well as unstable molecules entrapped in noble gas matrices. More recently, MCD has found useful application in the study of biologically important systems including metalloenzymes and proteins containing metal centers.
In natural optical activity, the difference between the LCP light and the RCP light is caused by the asymmetry of the molecules (i.e. chiral molecules). Because of the handedness of the molecule, the absorption of the LCP light would be different from the RCP light.
Source officielle
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