PRERESONANCE RAMAN EXCITATION PROFILES OF $CAROTENOIDS^{*}$

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1983

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Ohio State University

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It is now well established1 that the lowest excited singlet electronic state in linear polyenes of at least moderate Length has the same parity as the ground state, and is thus forbidden in normal one-photon absorption. The (allowed) 11Bu←11Ag transition energy reaches an asymptotic value for long polyene chains; however; the corresponding behaviour for the 21Ag←11Ag excitation has not been determined. In order to locate this ""hidden"" state in polyenes possessing 9−15C=C bonds, we are studying the preresonant Raman scattering from a series of carotenoids. The relative intensity of the C = C stretch of the solute to a neighbouring cyclohexane solvent made is measured as the exciting line is tuned through the region of interest. The presence of an underlying state is manifest by interference features on the Raman excitation profile,2 and we have interpreted the profile of β-carotene (n=9) accordingly,3 We report here corresponding measurements for lycopene (n = 11) and decapreno-βcarotene(n=13). Estimates of the 21Ag state origin based on these observations will be presented, and trends in the energy gaps with variation in chain length will be discussed. Research supported in part by the U. S. National Science Foundation. 1B. S. Hudson, B. E. Kohler and K. Schulten, in Excited States, Vol, C. E. C. Liz., ed. (Academic Press, New York, 1982). 2J. Friedman and R. M. Hochstrasser, Chem. Phys. Letters 32, 414 (1975). 3R. J. Thrash, H. K. L. -B. Fang and G. E. Leroi, J. Chem. Phys. 67, 5939 (1977).

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Author Institution: Department of Chemistry, Michigan State University

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