Photolysis

Photodissociation, photolysis, photodecomposition, or photofragmentation is a chemical reaction in which molecules of a chemical compound are broken down by photons. It is defined as the interaction of one or more photons with one target molecule.

Photodissociation is not limited to visible light. Any photon with sufficient energy can affect the chemical bonds of a chemical compound. Since a photon's energy is inversely proportional to its wavelength, electromagnetic radiations with the energy of visible light or higher, such as ultraviolet light, x-rays, and gamma rays can induce such reactions.

Photolysis in photosynthesis

Photolysis is part of the light-dependent reaction or light phase or photochemical phase or Hill reaction of photosynthesis. The general reaction of photosynthetic photolysis can be given in terms of photons as:
:$\ce + 2 \text \longrightarrow \ce$

The chemical nature of "A" depends on the type of organism. Purple sulfur bacteria oxidize hydrogen sulfide () to sulfur (S). In oxygenic photosynthesis, water () serves as a substrate for photolysis resulting in the generation of diatomic oxygen (). This is the process which returns oxygen to Earth's atmosphere. Photolysis of water occurs in the thylakoids of cyanobacteria and the chloroplasts of green algae and plants.

Energy transfer models

The conventional semi-classical model describes the photosynthetic energy transfer process as one in which excitation energy hops from light-capturing pigment molecules to reaction center molecules step-by-step down the molecular energy ladder.

The effectiveness of photons of different wavelengths depends on the absorption spectra of the photosynthetic pigments in the organism. Chlorophylls absorb light in the violet-blue and red parts of the spectrum, while accessory pigments capture other wavelengths as well. The phycobilins of red algae absorb blue-green light which penetrates deeper into water than red light, enabling them to photosynthesize in deep waters. Each absorbed photon causes the formation of an exciton (an electron excited to a higher energy state) in the pigment molecule. The energy of the exciton is transferred to a chlorophyll molecule (P680, where P stands for pigment and 680 for its absorption maximum at 680 nm) in the reaction center of photosystem II via resonance energy transfer. P680 can also directly absorb a photon at a suitable wavelength.

Photolysis during photosynthesis occurs in a series of light-driven oxidation events. The energized electron (exciton) of P680 is captured by a primary electron acceptor of the photosynthetic electron transport chain and thus exits photosystem II. In order to repeat the reaction, the electron in the reaction center needs to be replenished. This occurs by oxidation of water in the case of oxygenic photosynthesis. The electron-deficient reaction center of photosystem II (P680*) is the strongest biological oxidizing agent yet discovered, which allows it to break apart molecules as stable as water.

The water-splitting reaction is catalyzed by the oxygen evolving complex of photosystem II. This protein-bound inorganic complex contains four manganese ions, plus calcium and chloride ions as cofactors. Two water molecules are complexed by the manganese cluster, which then undergoes a series of four electron removals (oxidations) to replenish the reaction center of photosystem II. At the end of this cycle, free oxygen () is generated and the hydrogen of the water molecules has been converted to four protons released into the thylakoid lumen (Dolai's S-state diagrams).

These protons, as well as additional protons pumped across the thylakoid membrane coupled with the electron transport chain, form a proton gradient across the membrane that drives photophosphorylation and thus the generation of chemical energy in the form of adenosine triphosphate (ATP). The electrons reach the P700 reaction center of photosystem I where they are energized again by light. They are passed down another electron transport chain and finally combine with the coenzyme and protons outside the thylakoids to form NADPH. Thus, the net oxidation reaction of water photolysis can be written as:
:$\ce + 8 \text \longrightarrow \ce$

The free energy change () for this reaction is 102 kilocalories per mole. Since the energy of light at 700 nm is about 40 kilocalories per mole of photons, approximately 320 kilocalories of light energy are available for the reaction. Therefore, approximately one-third of the available light energy is captured as NADPH during photolysis and electron transfer. An equal amount of ATP is generated by the resulting proton gradient. Oxygen as a byproduct is of no further use to the reaction and thus released into the atmosphere.

Quantum models

In 2007 a quantum model was proposed by Graham Fleming and his co-workers which includes the possibility that photosynthetic energy transfer might involve quantum oscillations, explaining its unusually high efficiency.

According to Fleminghttps://phys.org/news/2007-04-quantum-secrets-photosynthesis-revealed.html Quantum secrets of photosynthesis revealed there is direct evidence that remarkably long-lived wavelike electronic quantum coherence plays an important part in energy transfer processes during photosynthesis, which can explain the extreme efficiency of the energy transfer because it enables the system to sample all the potential energy pathways, with low loss, and choose the most efficient one. This claim has, however, since been proven wrong in several publications.

This approach has been further investigated by Gregory Scholes and his team at the University of Toronto, which in early 2010 published research results that indicate that some marine algae make use of quantum-coherent electronic energy transfer (EET) to enhance the efficiency of their energy harnessing.

Photoinduced proton transfer

Photoacids are molecules that upon light absorption undergo a proton transfer