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Interference effects in natural circular dichroism spectra

โœ Scribed by Aage E. Hansen


Publisher
Elsevier Science
Year
1978
Tongue
English
Weight
398 KB
Volume
57
Category
Article
ISSN
0009-2614

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โœฆ Synopsis


Et is shown that Fano-type interference between a discrete (e-g_ Rydberg) transition and a continuous (e.g. valence shell) transition can lead to natural circuku dichroism line shapes whicS deviate significantly from shnpIe superposition. The resuits arc ilXustxted for a &iml moIecuIe of C, symmetry_ Ccmparisons between computed and measured signs and magnitudes of circular dichroism (CD) spectra are important both in the study of the structure of chiral rnoiecu!es, and in the assignment of spectral transitions. However such comparisons can be hampered by spectral congestion of strongly overlapping excitations_ We shall consider here the case of a discrete excitation (e-g_ of Rydberg type) embedded in an essentially continuous excitation (e-g_ the dense viironic manifold of a valence shell excitation) in a chiral moiecuie, and derive expressions for the resuhing CD line shapes which suggest that neglect of the interference between these excitations can Iead to misinterpretations of the chiroptical properties of the discrete exci'kation For ordinary absorption spectra such interference effects were frrst discussed by Fano [I] for autoionizing atomic transitions, and subsequently by a number of authors for moIecuhu and solid state systems, where the interference is usuahy assumed to be generated by viironic interactions (see e.g. refs. [2-101). For the chiroptical properties of chi.ral molecules the effect of tibronic coupling between discrete excitations has been studied in detail for many different coupling


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