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By Erik Waaben Thulstrup (auth.)

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Extra info for Aspects of the Linear and Magnetic Circular Dichroism of Planar Organic Molecules

Sample text

It was emphasized (70) that the results were obtained from only one assumption about the K's; however, the assumption of a rodlike orientation distribution for fluoranthene was made implicitly. The actual orientation distribution in the experiment did not have this property (Fig. 2) and application of the Fraser-Beer model led to incorrectly reduced spectra. Other examples of appl~cations of the Fraser- Beer model, where the rod-like orientation distributions assumed seem highly unlikely, are found in studies of carotenoids(71,72), and several other molecules (73-75).

The Fraser-Beer-model has been defended by some authors (49, 58, 71, 81, 82) by suggesting that since the polyethylene frequently used in LD experiments is composed of two regions, a crystalline and an amorphous, it is probable that the molecules incorporated are either perfectly oriented in the crystalline parts of the polyethylene or randomly oriented in the amorphous part. 5) and such high concentrations of guest molecules in the crystalline regions are very unlikely (83). Moreover, since f is usually much larger for elongated than for short molecules, the assumption imply that the former molecules tend to go into the crystalline regions much more easily than the latter, which seems highly improbable.

15612 included for the calculation of matrix elements of. the magnetic dipole moment operator. The agreement with experiment is reasonably good for the two calculations (1 I and 2) where approximate or perfect alternant pairing symmetry for the states is present. The agreement is clearly unsatisfactory in some cases, when alternant pairing has been completely removed (calc. 1). It should be emphasized that the price paid,when the inexpensive method (calc. 2) is used, is the lack of information about transition moments and MCD B-terms for transitions between states of the same pairing symmetry, the alternant pairing symmetry forbidden transitions.

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