Circular polarization, optical principles

The process by which a stereochemically inactive center is converted to a specific stereoisomeric form. In most cases, the reacting center is prochiral. Such processes can occur with reactions involving an optically active reagent, solvent, or catalyst (eg., an enzyme). The reaction produced by such a process is referred to as an enantioselective reaction. In principle, use of circularly polarized light in photochemical reactions of achiral reactants might also exhibit asymmetric induction. However, reported enantioselectivities in these cases have been very small. 

The relatively simple Rosenfeld equation (8.6) determines the relation between the structure of a molecule and its interaction with circularly polarized radiation. Different methods are used for the computation of R, including the direct calculation by ab initio methods from first principles. However, at least within a limited range of applications, simplified approaches can be used that make a priori assumptions about a decisive mechanism by which optical activity of a molecule originates. 

A unidirectionally aligned nematic or smectic liquid crystal phase can act as an optical retardation film. The same principle occurs with well-aligned LCP films which are being explored as compensation films for STN displays. Chiral nematic films also offer unique optical properties and in a polymeric form could he useful in converting ordinary light into circularly polarized light. 

The measurement of vibrational optical activity requires the optimization of signal quality, since the experimental intensities are between three and six orders of magnitude smaller than the parent IR absorption or Raman scattering intensities. To date all successful measurements have employed the principles of modulation spectroscopy so as to overcome short-term instabilities and noise and thereby to measure VOA intensities accurately. In this approach, the polarization of the incident radiation is modulated between left and tight circular states and the difference intensity, averaged over many modulation cycles, is retained. In spite of this common basis, there are major differences in measurement technique and instrumentation between VCD and ROA consequently, the basic experimental methodology of these two techniques will be described separately. 

Abstract In the first part of this chapter we will illustrate circular dichroism and we will discuss the optical activity of chemical compounds with respect to light absorption which is at the basis of this technique. Moreover, we will introduce the phenomena that lie behind the technique of optical rotatory dispersion. We thought appropriate to include a brief description of linear dichroism spectroscopy, although this technique has nothing to do with optical activity. In the final part of the chapter we will introduce the basic principles of the luminescence teehniques based on polarized (either circularly or linearly) excitation. The experimental approach to the determination of steady-state and time resolved fluorescence anisotropy will be illustrated. For all the teehniques examined in this chapter the required instrumentation will be schematieally deseribed. A few examples of application of these techniques to molecular and supramolecular systems will also be presented. 

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