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.
History 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.
Differences between CD and MCD 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. However, in MCD in the presence of a magnetic field, LCP and RCP no longer interact equivalently with the absorbing medium. Thus, there is not the same direct relation between magnetic optical activity and molecular stereochemistry which would be expected, because it is found in natural optical activity. So, natural CD is much more rare than MCD which does not strictly require the target molecule to be chiral. Although there is much overlap in the requirements and use of instruments, ordinary CD instruments are usually optimized for operation in the ultraviolet, approximately 170–300 nm, while MCD instruments are typically required to operate in the visible to near infrared, approximately 300–2000 nm. The physical processes that lead to MCD are substantively different from those of CD. However, like CD, it is dependent on the differential absorption of left and right hand circularly polarized light. MCD will only exist at a given wavelength if the studied sample has an optical absorption at that wavelength. This is distinctly different from the related phenomenon of optical rotatory dispersion (ORD), which can be observed at wavelengths far from any absorption band.
Measurement The MCD signal ΔA is derived via the absorption of the LCP and RCP light as
Δ A = A − − A + A − + A + {\displaystyle \Delta A={\frac {A_{-}-A_{+}}{A_{-}+A_{+}}}}
This signal is often presented as a function of wavelength λ, temperature T or magnetic field H. MCD spectrometers can simultaneously measure absorbance and ΔA along the same light path. This eliminates error introduced through multiple measurements or different instruments that previously occurred before this advent. The MCD spectrometer example shown below begins with a light source that emits a monochromatic wave of light. This wave is passed through a Rochon prism linear polarizer, which separates the incident wave into two beams that are linearly polarized by 90 degrees. The two beams follow different paths- one beam (the extraordinary beam) traveling directly to a photomultiplier (PMT), and the other beam (the ordinary beam) passing through a photoelastic modulator (PEM) oriented at 45 degrees to the direction of the ordinary ray polarization. The PMT for the extraordinary beam detects the light intensity of the input beam. The PEM is adjusted to cause an alternating plus and minus 1/4 wavelength shift of one of the two orthogonal components of the ordinary beam. This modulation converts the linearly polarized light into circularly polarized light at the peaks of the modulation cycle. Linearly polarized light can be decomposed into two circular components with intensity represented as I 0 = 1 2 ( I − + I + ) {\displaystyle I_{0}={\frac {1}{2}}(I_{-}+I_{+})}
The PEM will delay one component of linearly polarized light with a time dependence that advances the other component by 1/4 λ (hence, quarter-wave shift). The departing circularly polarized light oscillates between RCP and LCP in a sinusoidal time-dependence as depicted below:
The light finally travels through a magnet containing the sample, and the transmittance is recorded by another PMT. The schematic is given below:
The intensity of light from the ordinary wave that reaches the PMT is governed by the equation:
… excerpt ends here. Continue reading the full article.
