Journal of Physical Chemistry B, Vol.101, No.22, 4448-4457, 1997
Electron-Phonon Coupling and Vibronic Fine-Structure of Light-Harvesting Complex-II of Green Plants - Temperature-Dependent Absorption and High-Resolution Fluorescence Spectroscopy
Polarized, site-selected fluorescence was measured for light-harvesting complex II (LHCII), the major Chi a/b/xanthophyll binding light-harvesting complex of green plants. Upon selective excitation in the range of 679-682 nm at 4 K, separate zero-phonon lines and phonon wings could be observed, as well as sharp lines in the vibronic region of the emission : vibronic zero-phonon lines. The maximum of the phonon wing was located 22 cm(-1) to the red of the zero-phonon line. Forty-eight vibrational modes could be identified, and their Franck-Condon factors were estimated. From the vibrational frequencies it is concluded that the Chi a responsible for the emission at 4 K is monoligated and accepts a hydrogen bond on the 13(1)-keto group. Also measured was the temperature dependence of the absorption spectrum of LHCII. Using the phonon wing obtained from the fluorescence measurements and an algorithm based on linear, harmonic Franck-Condon electron-phonon coupling and temperature independent inhomogeneous broadening, the temperature dependence of the low-energy part of the Q(r) absorption spectrum could be simulated very well up to 220 K. Above this temperature, the simulated and experimental results start to deviate. : vibronic zero-phonon lines. The maximum of the phonon wing was located 22 cm(-1) to the red of the zero-phonon line. Forty-eight vibrational modes could be identified, and their Franck-Condon factors were estimated. From the vibrational frequencies it is concluded that the Chi a responsible for the emission at 4 K is monoligated and accepts a hydrogen bond on the 13(1)-keto group. Also measured was the temperature dependence of the absorption spectrum of LHCII. Using the phonon wing obtained from the fluorescence measurements and an algorithm based on linear, harmonic Franck-Condon electron-phonon coupling and temperature independent inhomogeneous broadening, the temperature dependence of the low-energy part of the Q(r) absorption spectrum could be simulated very well up to 220 K. Above this temperature, the simulated and experimental results start to deviate.
Keywords:CHLOROPHYLL-A;PHOTOSYSTEM-II;CHLOROPLAST MEMBRANES;BINDING-PROTEIN;ANTENNA COMPLEX;RESONANCE RAMAN;LHC-II;SPECTRA;MOLECULES;DYNAMICS