Analytical formulas for low-fluence non-line-narrowed hole-burned spectra in an excitonically coupled dimer

We present exact equations for the low-fluence non-line-narrowed (NLN) nonphotochemical hole-burning (NPHB) spectrum of an excitonically coupled dimer (for arbitrary coupling strength) under the assumption that postburn and preburn site energies are independent. The equations provide a transparent view into the contributions of various effects to the NPHB spectrum. It is demonstrated that the NPHB spectrum in dimers is largely dominated by the statistical reshuffling of site energies and by altered excitonic transition energies of both excitonic states (in contrast with only the lowest state). For comparison of these results with those from larger excitonically coupled systems, the low-fluence NLN NPHB spectrum obtained for the CP47 complex (a 16-pigment core antenna complex of Photosystem II) is also calculated using Monte Carlo simulations. In this larger system it is shown that the NPHB spectra for individual excitonic states are not entirely conservative (although the changes in average oscillator strength for the higher excitonic states are in most cases less than 1%), a feature which we argue is due primarily to reordering of the contributions of various pigments to the excitonic states. We anticipate that a better understanding of NPHB spectra obtained for various photosynthetic complexes and their simultaneous fits with other optical spectra (e.g., absorption, emission, and circular dichroism spectra) will provide more insight into the underlying electronic structures of various photosynthetic systems.