A theory is presented for the temperature dependence of the absorption and hole-burned spectra of chromophores imbedded in solids characterized by structural heterogeneity. The theory is applicable for arbitrarily strong linear electron-phonon coupling and describes the overall hole profile which consists of the zero-phonon hole and its associated phonon sideband hole structure. A novel and convenient form for the thermally averaged Franck-Condon factors is employed. Illustrative calculations are presented which pertain to the temperature dependence of the absorption band of the primary electron donor of the photosynthetic bacterial reaction center and the design of high-temperature hole-burning materials for high-density frequency domain optical storage.

No abstract

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.

Persistent photochemical hole burned profiles are reported for the primary electron donor state P700 of the reaction center of PS I. The hole profiles at 1.6 K for a wide range of burn wavelengths (λB) are broad (FWHM∼310 cm(-1)) and for the 45:1 enriched particles studied exhibit no sharp zero-phonon hole feature coincident with λB. The λB hole profiles are analyzed using the theory of Hayes et al. [J Phys Chem 1986, 90: 4928] for hole burning in the presence of arbitrarily strong linear electron-phonon coupling. A Huang-Rhys factor S in the range 4-6 and a corresponding mean phonon frequency in the range 35-50 cm(-1) together with an inhomogeneous line broadening of∼100 cm(-1) are found to provide good agreement with experiment. The zero-point level of P700(*) is predicted to lie at∼710 nm at 1.6K with an absorption maximum at∼702 nm. The hole spectra are discussed in the context of the hole spectra for the primary electron donor states of PS II and purple bacteria.