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FREE-ELECTRON MODEL sponsible for these absorption bands have been labeled by Klevens and Platt 105 as lA —> xLh, lA —> lLa) and lA —> ^ transitions, respectively, where l A represents the ground state of the molecule and 1Lb, 1La, and ^ ( d e ­ generate) are excited singlet states. The oscillator strength of a lA —> lLa transition generally is almost two orders of magnitude greater than a l A —> lLb transition and an order of magnitude less than the lA —»1B transition. Transitions from the ground state to lL states are said to be symmetry-forbidden transitions and to 1B states, allowed transitions.

Moments of suitably substi­ tuted 9,9 , -bianthryls were measured to determine the angle between the chromophores. Angles of 70°, 61°, and 56° were measured for 2,2 / -bifluorobianthryl, 2,2 , -bichlorobianthryl, and 2,2 / -bibromobianthryl, respectively. b. EFFECT OF PLANARITY ON FLUORESCENCE SPECTRUM Molecular structure plays a major role in determining the characteristic shape and wavelength position of the fluorescence spectrum. Planar mole- 50 3. GENERAL INFORMATION cules with high degrees of symmetry have absorption and fluorescence spectra with well resolved vibrational bands.

A constant spatial orientation of the components of a chromophore, it appears that rigidity per se is not the important factor, but rather rigidity in maintaining a planar or near planar configuration. As an example, as-stilbene is known to have practically zero fluorescence quantum yield at room temperature, yet phenanthrene which can be considered as a bridged derivative of m-stilbene with greater rigidity has a much larger quantum yield. It is also informative to compare the planar and rigid compound triphenylene (#182C) with the nonplanar and "loose" compound o-terphenyl whose fluorescence quantum yield is almost nil.

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Baumjohann, Basic spase plasma physics


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