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Each diagonal term k,, of each row in Eq. 5.1-19 represents the absorption coefficient of the component i for which the respective band with wavenumber G, with the absorbance A; was chosen. If the bands have been selected appropriately (none or negligible overlapping from bands of other constituents of the sample), this diagonal term is large, whereas the off-diagonal elements (which represent the fraction of A, from the other constituents) are small or even zero. Nevertheless, these off-diagonal coefficients represent absorptions of the other components which contribute to the chosen band. If the absorption coefficients at the chosen wavenumber positions have been determined for each constituent of the sample, the concentrations c, of these constituents may be determined by solving the linear equations using standard methods of matrix algebra. If there are only two compounds in a sample, then

The chirality of the cholesteric structure and the dispersion-like rotation spectrum similar to a Cotton effect, suggest that this should be called optical activity, especially optical rotation This latter can be considered as circular birefringence, ie, different refractive indices for left and right circular polarized radiation However, already the term optical rotatory dispersion might be misleading since in conventional interpretation this would demand for an accompanying circular-dichroism band Leaving reflection completely out of consideration, transmittance spectra could be mistaken to support this assumption However, the intensity missing in the transmission spectrum was reflected, absorption might totally be absent, and all phenomena disappear upon transition of the sample into the isotropic state as also shown in Fig 46-10 This indicates that selective reflection is based on the cholesteric order and thus, on the structure of this phase, so that some type of interference might be responsible.

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In any case, the phenomena stated here are not related to VCD and VORD (eg Nafie, 1984), the vibrational-transition based analogues to circular dichroism (CD) and optical rotatory dispersion of optically active compounds in the ultraviolet and visible range which all are observed in isotropic state (eg Mason, 1982) There should be closer similarities to the optical activity of helical polymers as far as models such as copper wire helices are applicable (Tinoco and Freeman, 1975) The cholesteric selective reflection is often associated with Bragg reflection (Elser and Ennulat, 1976; Schadt, 1993a) However, an effect which is quite similar from a different point of view, is exploited in high-power laser applications: The dielectric mirror consisting of a stack of thin, transparent layers of basically two materials in alternating sequence.

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Such a stratified medium (Born and Wolf, 1980) acts as a highly efficient mirror in a certain spectral interval only Compiling it from suitably birefringent materials a linear analogue of the cholesteric behaviour can be formulated (Korte et al, 1994) As early as in 1951 de Vries showed that a twisted stack of birefringent layers is an adequate model for a cholesteric structure in order to reproduce a principally correct spectral dependence of the optical rotation also around the selective reflection band as it was recorded in a different way for Fig 46-8 Even if the layer thickness is formally reduced to zero the optical rotation and its spectral dependence is preserved Several other approaches were reported to describe particular effects of the cholesteric structure such as the selective reflectance or the rotatory anomaly (eg Chandrasekhar and Prasad, 1971; Chandrasekhar and Ranganath, 1974; Schonhofer et al.

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