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• W1991998372 abstract "FEW properties of matter can rival optical rotatory power as a potential means of gaining information about the more subtle aspects of molecular structure. Optical rotation is especially sensitive to such structural factors as the spatial conformation of a hydrocarbon chain in an asymmetric molecule and the existence of a six-membered ring in one or the other of the chair forms or bed forms. It is also easy to measure, it is not affected to any unusual extent by impurities, and the apparatus for measuring it is readily available. Furthermore, the theoretical principles that underlie the phenomenon are well understoodinageneral way. Rosenfeld’s quantum mechanical equation for optical rotation specifies the fundamental molecular quantities responsible for the phenomenon and shows that it is dependent on the properties of the electronic transitions that give rise to visible and ultra-violet spectra. The more detailed models of Kuhn, Kirkwood and Condon and Eyring present us with specific ways in which the rotatory properties are related to molecular structure and conformation. These theories have been useful in the interpretation of rotatory dispersion, circular dichroism the role of weak absorption bands, and the effects of solvents and temperature. Unfortunately the use of optical rotation has not yet reached the level of importance that it deserves. The principal reason for this is that we do not yet have a sufficiently reliable and detailed understanding of the relationship between the optical rotation and molecular structure-an understanding, that is, which would permit us to predict with confidence the sign and magnitude of the rotation to be expected for a given molecule in a given configuration and conformation. All of the existing theories require such drastic approximations when one attempts to use them to calculate a numerical value of the rotation that one can have little confidence in them for this purpose. Furthermore, there is no reason to expect any great improvement in the current theories in this respect in the near future. At the present time, therefore, the only hope of success in relatingoptical rotation to molecular structure seems to lie in a more empirical approach. Such an approach has been attempted by a number of workers with varying and uncertain success. One of the earliest attempts was the van? Hoffprinciple of superposition, which we now know cannot be valid except in certain limited circumstances. More recently Marke? Whiffen and BrewstetS have given discussions of the signs and magnitudes of optical rotations which are encouraging, although the general validity of the principles that they have proposed still remains to be demonstrated." @default.
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• W1991998372 date "1961-01-01" @default.
• W1991998372 modified "2023-10-03" @default.
• W1991998372 title "The principle of pairwise interactions as a basis for an empirical theory of optical rotatory power" @default.
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• W1991998372 doi "https://doi.org/10.1016/s0040-4020(01)92205-7" @default.
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