Magnetic circular dichroism

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Magnetically induced Circular Dichroism (MCD) is the differential absorption of left and right circularly polarized light, induced in a sample by a strong magnetic field oriented parallel to the direction of light propagation. In general, this means wrapping a circular dichrometer in a large electromagnet. If the magnet is water cooled, field strength of a couple of teslas are common. With a superconducting magnet, field strengths can reach 7 Teslas.

It was first shown by Faraday that optical activity could be induced in matter by a longitudinal magnetic field (a field in the direction of light propagation) [1]. 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.[2][3]

The main focus of the MCD is to analyze the A, B, C terms of the spectra. Principles and examples will be explained later on this page.

Contents

Applicable Cases

MCD can be used as an optical technique for the detection of electronic structure of both the ground states and excited states. It is also a strong addition to the more commonly used absorption spectroscopy, and there are two reasons that explain this. First, a transition buried under a stronger transition can appear in MCD if the first derivative of the absorption is much larger for the weaker transition or it is of the opposite sign. Second, MCD will be found where no absorption is detected at all if ΔA > (ΔAmin) but A<Amin, where (ΔA)min and Amin are the minimum of ΔA and A that are detectable. Typically, (ΔAmin) and Amin are of the magnitudes around 10−5 and 10−3 respectively. So, a transition can only be detected in MCD, not in the absorption spectroscopy, if ΔA/A > 10−2. This happens in paramagnetic systems that are at lower temperature or that have sharp lines in the spectroscopy.[4]

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