Download PDF by Erik Waaben Thulstrup (auth.): Aspects of the Linear and Magnetic Circular Dichroism of

By Erik Waaben Thulstrup (auth.)

ISBN-10: 3540097546

ISBN-13: 9783540097549

ISBN-10: 3642931367

ISBN-13: 9783642931369

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

Example text

This consequence of Tanizaki's model is obviously physically unacceptable. 40 6c. Other assumptions of orientation distributions. For many years, two of the pioneers in the field of LD spectroscopy, Popov and Smirnov, preferred to consider the information obtained from stretched sheet spectra as qualitative information (110-13). In 1970 Popov proposed an orientation model (114-16) that made a quantitative determination possible of the angle ¢i between the orientation axis and the transition moment for the i'th transition: where g(~i) tion at ~i is the ratio LEZ(~i)-EY(~i)l/~z(~i)+EY(~i)lfor the transi- and A is an orientation constant for a given molecule and degree of stretching.

Ously, . the quanti ties (III,31) Kz/K~ and Ky/K~ may be determined from (III,31) when z- and y-polarized spectral features can be identified in the spectrum, since: From (III,31) it is clear that the reduced spectra AZ{A) and Ay{A) can be written (6, 19): C [EZ{A}-{K IK')Ey{A)] z Y Y (III,32) where C z and Cy are constants, which depend on K , K', K , and K'. Their z z y y size cannot be determined from the observed spectra EZ{A) and Ey{A). However, their relative size may be determined by comparison with a spectrum of a sample with random orientation A{A), since where C is an unknown constant.

L CALC. l' • CALC. 1 2 CALC. EXP. B CALC. b CALC. CALC. l' 1 2 EXP. CALC. l' • CALC. 1 2 B CALC. 5 f POL. 3 POL. 6 f POL. 5 POL. 7 Y Y Y Y ), oscillator strength (f), transition moment directions (POL) and MCD B-terms (B in -3 2 -1 10 SeD /cm ) are from (6, 151). The calculated results have been obtained according to the methods calc. 1, calc. 1 I and calc. 2 described in the text (147). 58 support for the procedure is found in the recent theoretical work by Michl (151, 152). It may be added that an interesting theoretical discussion of Hamiltonians used for descriptions of the MCD effect is found in ref.

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Aspects of the Linear and Magnetic Circular Dichroism of Planar Organic Molecules by Erik Waaben Thulstrup (auth.)

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