The Electronic Origin of Far‐Red‐Light‐Driven Oxygenic Photosynthesis

Photosystem‐II uses sunlight to trigger charge separation and catalyze water oxidation. Intrinsic properties of chlorophyll a pigments define a natural “red limit” of photosynthesis at ≈680 nm. Nevertheless, charge separation can be triggered with far‐red photons up to 800 nm, without altering the nature of light‐harvesting pigments. Here we identify the electronic origin of this remarkable phenomenon using quantum chemical and multiscale simulations on a native Photosystem‐II model. We find that the reaction center is preorganized for charge separation in the far‐red region by specific chlorophyll–pheophytin pairs, potentially bypassing the light‐harvesting apparatus. Charge transfer can occur along two distinct pathways with one and the same pheophytin acceptor (Pheo(D1)). The identity of the donor chlorophyll (Chl(D1) or P(D1)) is wavelength‐dependent and conformational dynamics broaden the sampling of the far‐red region by the two charge‐transfer states. The two pathways rationalize spectroscopic observations and underpin designed extensions of the photosynthetically active radiation limit.