Three pulse photon echo peak shift study of the B800 band of the LH2 complex of Rps. acidophila at room temperature: A coupled master equation and nonlinear optical response function approach
R. Agarwal et al., Three pulse photon echo peak shift study of the B800 band of the LH2 complex of Rps. acidophila at room temperature: A coupled master equation and nonlinear optical response function approach, J PHYS CH B, 105(9), 2001, pp. 1887-1894
Three pulse photon echo peak shift (3PEPS) data were obtained for the B800
band of Rps, acidophila (strain 10050) at room temperature. The peak shift
decays on two time scales: a sub 100 fs decay owing to the ultrafast solvat
ion by the protein bath and a 500-600 fs decay to a value of 2.5 fs at 1.2
ps. Here we present a novel method that properly incorporates the effect of
energy transfer on the nonlinear response functions to simulate the peak s
hift for weakly coupled, multi-chromophoric energy transfer systems. The me
thod involves calculation of third-order response functions for energy tran
sfer systems to account for the interaction of the laser pulses with the ch
romophores, whereas the energy transfer kinetics is incorporated by solving
the master equation for the whole ring of B800 pigments. The effect of dis
order on spectral overlaps is taken into account by a Monte Carlo sampling
procedure that selects transition frequencies from a Gaussian distribution
of site energies. The peak shift is then calculated by combining ensemble-a
veraged population kinetics with the appropriate response functions. We est
imate the energy transfer time within the B800 band to be similar to 500-60
0 fs, acid the experiments are well described by Forster theory level calcu
lations including energy disorder. By simultaneously modeling the peak shif
t data and the linear absorption spectrum, we suggest the presence of two l
evels of disorder (i.e., partially correlated disorder) in the B800 band. S
trong beats are also found in our data with a frequency of 165 cm(-1).