Excitonic states in photosystem II reaction center.

The excited states of a structurally well-determined photosystem II (PSII) reaction center are obtained using an effective Hamiltonian for the interaction between the Q(y) states. The latter are calculated using the time-dependent density functional theory (DFT) method in DFT-optimized geometries, but with conserved side group orientations. Of particular importance is the orientation of the vinyl group of ring I. Couplings are calculated using actual transition charge distributions via the INDO/S model. Good agreement with experimental spectra is obtained. The lowest excited state is mainly located on the inactive B-side, but with a large component on P(A) too, making charge separation to H(A) possible at low temperature. The "trap state" and triplet state are localized on the inactive B-side. Since the spin singlet Q(y) states of the reaction center are all within a rather small energy range, the state with the highest component of B(A)*, on the blue side of the Q(y) absorption, has a rather high Boltzmann population at room temperature. The charge-transfer states, however, have a rather large spread and cannot be calculated accurately at present. The orientation of the phytyl chains is important and has as a consequence that the energy for the charge-separated B(A)+ H(A)- state is significantly lower than the corresponding state on the B-side. It follows that the B(A)* and P(A)* states are both possible origins for a fast charge separation in PSII.