화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.106, No.14, 3566-3579, 2002
Changes in molecular structure upon triplet excitation of all-trans-spheroidene in n-hexane solution and 15-cis-spheroidene bound to the photo-reaction center from Rhodobacter sphaeroides as revealed by resonance-Raman spectroscopy and normal-coordinate analysis
The So and T-1 Raman spectra of all-trans-spheroidene and its deuterio derivatives (10-d, 12-d, 14-d, 15-d, 15'-d, 14'-d, and 15,15'-d(2)) were recorded in n-hexane solution. The T, state was generated by the use of a sensitizer, anthracene. An empirical normal-coordinate analysis of the spectral data was performed by using Urey -Bradley - Shimanouchi force field; non-UBS cross terms were also introduced. By the use of each carbon-carbon stretching force constant as a scale of bond order, large changes in bond order upon triplet excitation were identified in the central part of the conjugated chain: decrease in bond order was in the order, C13=C14 > C11=C12 > C9=C10 > C15=15', whereas increase in bond order was in the order, C12-C13 > C14-C15 approximate to C14'-CI5'. In other words, the triplet-excited region where the largest changes in bond order take place was located, not at the center of the entire carbon skeleton, but at the center of the conjugated chain. The So and T, Raman spectra of 15-cis-spheroidene and its deuterio derivatives (12-d, 14-d, 15-d, 15'-d, 14'-d and 15,15'-d2) incorporated into the photoreaction center from Rhodobacter sphaeroides R26 were also recorded. The T, state of spheroidene was generated by excitation of bacteriochlorophyll at the Q, absorption and subsequent triplet-energy transfer to the carotenoid. The S-0- and T-1-state carbon-carbon stretching force constants showed changes in bond order similar to those of all-trans-spheroidene in solution. However, empirical and normal-coordinate analysis of the T, Raman spectra showed twistings around the C15=C15', C13=C14 and C11=C12 bonds, the values of which were temporarily estimated to be +45degrees, -30degrees and +30degrees, respectively. A hypothetical mechanism of triplet-enerpy dissipation triggered by rotational motion around those double bonds has been proposed.