Cotunneling-Assisted Redistribution of Nonpassivity in a Photosynthetic Junction

Abstract

We investigate how cotunneling affects passive-state ordering in a Photosystem II reaction center modelled as a nonequilibrium molecular junction. We use a full pigment excitation manifold, with excitonic and charge-transfer rates computed within a Nakajima-Zwanzig formalism using realistic spectral densities. Cotunneling is introduced through a microscopically constructed doubly reduced acceptor state obtained from relevant quinone-side two-electron configurations, while photoexcitation is allowed into the full excitonic manifold. Passive-state permutations are quantified through ergotropy and energetic capacitance. We find that thermodynamic smoothness in ergotropy and energetic capacitance can conceal microscopic state rearrangements. Cotunneling redistributes the extractable nonequilibrium energy among the quinone acceptor, the donor-pheophytin radical pair, and excitonic states with strong contributions from pigments on the inactive branch. At high Coulomb interaction, cotunneling produces no passive-state reordering. Piecewise-linear relations among ergotropy, energetic capacitance, and mean energy further reveal the population reorderings generated by cotunneling.