Hole burning with pressure and electric field: A window on the electronic structure and energy transfer dynamics of bacterial antenna complexes

Abstract

Light-harvesting (LH) complexes of cyclic (C{sub n}) symmetry from photosynthetic bacteria are studied using absorption and high pressure- and Stark-hole burning spectroscopies. The B800 absorption band of LH2 is inhomogeneously broadened while the B850 band of LH2 and the B875 band of the LH1 complex exhibit significant homogeneous broadening due to ultra-fast inter-exciton level relaxation. The B800{r_arrow}B850 energy transfer rate of ({approximately}2 ps){sup {minus}1} as determined by hole burning and femtosecond pump-probe spectroscopies, is weakly dependent on pressure and temperature, both of which significantly affect the B800-B850 energy gap. The resilience is theoretically explained in terms of a modified Foerster theory with the spectral overlap provided by the B800 fluorescence origin band and weak vibronic absorption bands of B850. Possible explanations for the additional sub-picosecond relaxation channel of B800 observed with excitation on the blue side of B800 are given. Data from pressure and temperature dependent studies show that the B800 and B850 bacteriochlorophyll a (BChl a) molecules are weakly and strongly excitonically coupled, respectively, which is consistent with the X-ray structure of LH2. The B875 BChl a molecules are also strongly coupled. It is concluded that electron-exchange, in addition to electrostatic interactions, is important for understanding the strong coupling of the B850 and B875 rings. The large linear pressure shifts of {approximately}{minus}0.6 cm{sup {minus}1}/MPa associated with B850 and B875 can serve as important benchmarks for electronic structure calculations.