Energy-transfer and charge-separation pathways in the reaction center of photosystem II revealed by coherent two-dimensional optical spectroscopy.

The excited state dynamics and relaxation of electrons and holes in the photosynthetic reaction center of photosystem II are simulated using a two-band tight-binding model. The dissipative exciton and charge carrier motions are calculated using a transport theory, which includes a strong coupling to a harmonic bath with experimentally determined spectral density, and reduces to the Redfield, the Förster, and the Marcus expressions in the proper parameter regimes. The simulated third order two-dimensional signals, generated in the directions -k(1)+k(2)+k(3), k(1)-k(2)+k(3), and k(1)+k(2)-k(3), clearly reveal the exciton migration and the charge-separation processes.