Excitation transport and trapping on spectrally disordered lattices.
It is widely assumed that the decay of fluorescence in photosynthetic systems can be described as a sum of exponential components and that the amplitude of each component is directly related to the absorption cross-section of the antenna pigments coupled to the fluorescing species. We present exact calculations of excited state decay in two-dimensional regular lattices of different geometries containing multiple spectral forms of antenna pigments. We illustrate by these calculations that there is no simple relation between the decay amplitudes (and resulting time-resolved excitation spectra) and the steady-state absorption spectra. Only in the limit that the electronic excitations reach a rapid equilibrium among all antenna spectral forms does the excitation spectrum depend uniquely on the spectral features of the array. Using the simulations in conjunction with our recent fluorescence studies, we examine excitation transport and trapping dynamics in photosystem I and the limitations imposed by the finite time resolution in single photon counting experiments. In particular, we show that rising components, associated with excitation transfer among different spectral forms, with lifetimes <20 ps would be undetected in a typical photon counting experiment.
Department of Chemistry and the James Franck Institute, The University of Chicago, Chicago, Illinois 60637.
J M
JM
Jean
C K
CK
Chan
G R
GR
Fleming
T G
TG
Owens