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 StuartM. VengrisV. I. NovoderezhkinR. J. CogdellC. N. HunterR. 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. © 2011 American Chemical Society.