Abstract
Structural factors that provide localization of excited states and determine the properties of primary donor and acceptor of electron in the reaction center of photosystem II (PSII RC) are studied. The results of calculations using stationary and time-dependent density functional theory indicate an important role of protein environments of chlorophylls PA, PB, BA, and BB and pheophytins HA and HB in the area with a radius of no greater than ≤10 Å in the formation of excitonic states of PSII RC. When the neighboring elements are taken into account, the wavelength of long-wavelength Q y transition of chlorophyll molecules is varied by about 10 nm. The effect is less developed for pheophytin molecules (Δλ ≅ 2 nm). The following elements strongly affect energy of the transition: HisA198 and HisD197 amino-acid residues that serve as ligands of magnesium atoms affect PA and PB, respectively; MetA183 affects PA; MetA172 and MetD198 affect BA; water molecules that are located above the planes of the BA and BB macrocycles form H bonds with carbonyl groups; and phytol chains of PA and PB affect BA, BB, HA, and HB. The analysis of excitonic states, mutual positions of molecular orbitals of electron donors and acceptors, and matrix elements of electron transfer reaction shows that (i) charge separation between BA and HA and PB and BA is possible in the active A branch of cofactors of PSII RC and (ii) electron transfer is blocked at the BB - HB fragment in inactive B branch of PSII RC.
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Original Russian Text © E.E. Shchupak, N.V. Ivashin, 2014, published in Optika i Spektroskopiya, 2014, Vol. 116, No. 2, pp. 248–260.
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Shchupak, E.E., Ivashin, N.V. Spectral properties of chlorines and electron transfer with their participation in the photosynthetic reaction center of photosystem II. Opt. Spectrosc. 116, 228–238 (2014). https://doi.org/10.1134/S0030400X14020210
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DOI: https://doi.org/10.1134/S0030400X14020210