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

By Erik Waaben Thulstrup (auth.)

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5. The orientation triangle. A convenient way of illustrating the orientation of molecules in aniosotropic solvents and the relation between the K's is the orientation triangle (Fig. 2). The sides of the triangle, which describes the limiting values of (Kz,K y ) are: Ky Ky Ky Kz ,K x = (1-K z )/2 (disc-like orientation, d z = d Y) (1-K z )/2 K, (rod-like orientation, d y = d x ) x 1-K z ' Kx 0, (perfect alignment of the molecular planes with the stretching direction, d x = 0) . The lower left vertex (1/3, 1/3) may be obtained from a randomly orientated sample, the upper vertex (1/2, 1/2) from a sample of perfectly aligned disc-shaped molecules, while the lower right vertex (1,0) is obtained from perfect alignment of the orientation axis.

G. benzene and coronene). 9) be aligned completely differently. 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.

Included only for the calculation of matrix elements of These terms are not taken into account in connection with the determination of the wavefunctions, where they without inclusion of other similar terms are likely to cause a too strong breakdown of the alternant pairing symmetry. 1S12 (150). The non-neighbor terms are therefore most important when the contributions from S12 vanish, as they do for the calculation of matrix elements of M in a case of perfect pairing symmetry. Additional 57 Table 3.

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