Lowest Electronic States of the CP47 Antenna Protein Complex of Photosystem II: Simulation of Optical Spectra and Revised Structural Assignmentst

In this work, we present simulated steady-state absorption, emission, and nonresonant hole burning (HB) spectra for the CP47 antenna complex of photosystem II (PS II) based on fits to recently refined experimental data (Neupane et al. J. Am. Chem. Soc. 2010, 132, 4214). Excitonic simulations are based on the 2.9 angstrom resolution structure of the PS II core from cyanobacteria (Guskov et al. Nut. Struct. Mol. Biol. 2009, 16, 334), and allow for preliminary assignment of the chlorophylls (Chls) contributing to the lowest excitonic states. The search for realistic site energies was guided by experimental constraints and aided by simple fitting algorithms. The following experimental constraints were used: (i) the oscillator strength of the lowest-energy state should be approximately <= 0.5 Chl equivalents; (ii) the excitonic structure must explain the experimentally observed red-shifted (similar to 695 nm) emission maximum; and (iii) the excitonic interactions of all states must properly describe the broad (non-line-narrowed, NLN) HB spectrum (including its antihole) whose shape is extremely sensitive to the excitonic structure of the complex, especially the lowest excitonic states. Importantly, our assignments differ significantly from those previously reported by Raszewski and Renger (J. Am. Chem. Soc. 2008, 130, 4431), due primarily to differences in the experimental data simulated. In particular, we find that the lowest state localized on Chl 526 possesses too high of an oscillator strength to fit low-temperature experimental data. Instead, we suggest that Chl 523 most strongly contributes to the lowest excitonic state, with Chl 526 contributing to the second excitonic state. Since the fits of nonresonant holes are more restrictive (in terms of possible site energies) than those of absorption and emission spectra, we suggest that fits of linear optical spectra along with HB spectra provide more realistic site energies.