Journal of Physical Chemistry B, Vol.105, No.36, 8607-8615, 2001
Optical dephasing in the light-harvesting complex II: A two-pulse photon echo study
Time-resolved and integrated two-pulse photon echo signals were measured at 5 K in the wavelength range from 640 to 690 nm (with an increment of 5 nm) in samples of solubilized light-harvesting complex Il (LHC II) from spinach. Furthermore, the dephasing time was determined at 680 nm in the temperature range 5 T less than or equal to 300 K. The following results and conclusions were gathered from these experiments: (a) the photon echo intensity as a function of the temporal distance between both excitation pulses exhibits a nonexponential decay; (b) data analysis on the basis of a superposition of several dephasing processes leads to three characteristic dephasing time domains (A, B, and C) with markedly different wavelength dependencies of dephasing time and relative amplitude, T-2(A) less than or equal to 1.7 ps from 640 to 675 nm, T-2(B) = 4-13 ps over the whole wavelength region of 640 to 690 mn, and T-2(c) greater than or equal to 40 ps from 675 to 685 nm; (c) the dephasing times T-2(A) and T-2(B) are attributed to the kinetics of excitation energy transfer and to multiexciton processes above 670 nm, and (d) the longest dephasing time T-2(C) reaches values up to 350 ps at 684 nm. The temperature dependence of the dephasing rate (T2(c))(-1) at 680 nm is characterized by two different domains: below 20 K the rate steeply decreases due to pure dephasing, similar to the well-known T-1.3 dependence of the homogeneous line widths at low temperatures in organic glasses. At temperatures above 20 K a linear increase of (T-2(C))(-1) with temperature and a comparatively weak slope are observed, ascribed to uphill energy transfer. The results obtained in this study are discussed in comparison with data in the literature that were gathered from hole burning, transient absorption measurements, and spectra simulations.