Applications of spectral hole burning spectroscopies to antenna and reaction center complexes

The underlying principles of spectral hole burning spectroscopies and the theory for hole profiles are reviewed and illustrated with calculated spectra. The methodology by which the dependence of the overall hole profile on burn wavelength can be used to reveal the contributions from site inhomogeneous broadening and various homogeneous broadening contributions to the broad Qy-absorption bands of cofactors is emphasized. Applications to the primary electron donor states of the reaction centers of purple bacteria and Photosystems I and II of green plants are discussed. The antenna (light harvesting) complexes considered include B800-B850 and B875 of Rhodobacter sphaeroides and the base-plate complex of Prosthecochloris aestuarii with particular attention being given to excitonic interactions and level structure. The data presented show that spectral hole burning is a generally applicable low temperature approach for the study of excited state electronic and vibrational (intramolecular, phonon) structures, structural heterogeneity and excited state lifetimes.