Journal of Physical Chemistry A, Vol.115, No.16, 3834-3844, 2011
Dynamics of Exciton Relaxation in LH2 Antenna Probed by Multipulse Nonlinear Spectroscopy
We explain the relaxation dynamics in the LH2-B850 antenna as revealed by multipulse pump-dump-probe spectroscopy (Th.A. Cohen Stuart, M. Vengris, V.I. Novoderezhkin, R.J. Cogdell, C. N. Hunter, R. van Grondelle, submitted,. The theory of pump-dump-probe response is evaluated using the doorway window approach in combination with the modified Redfield theory. We demonstrate that a simultaneous fit of linear spectra, pump probe, and pump-dump-probe kinetics can be obtained at a quantitative level using the disordered exciton model,;which is essentially the Same as used to model the spectral fluctuations in single LH2 complexes (Novoderezhkin, V.; Rutkauskas, D.; van Grondelle, R. Biophys. J. 2006, 90, 2890). The present studies suggest that the observed relaxation rates are strongly dependent on the realization of the disorder. A big spread of the rates (exceeding 3 orders of magnitude) is correlated with the disorder-induced changes in delocalization length and overlap of the exciton wave functions : We conclude that the bulk kinetics reflect a superposition of many pathways corresponding to different physical limits of energy transfer, varying from sub-20 fs relaxation between delocalized and highly spatially overlapping exciton states to > 20 ps jumps between states localized at the opposite sides of the ring.