Photodissociation, photolysis, or photodecomposition is a chemical reaction in which a chemical compound is 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 waves with the energy of visible light or higher, such as ultraviolet light, x-rays and gamma rays are usually involved in such reactions.
Photolysis in photosynthesisPhotolysis is part of the light-dependent reactions of photosynthesis. The general reaction of photosynthetic photolysis can be given as H2A + 2 photons (light) → 2 e− + 2 H+ + A The chemical nature of "A" depends on the type of organism. In purple sulfur bacteria, hydrogen sulfide (H2S) is oxidized to sulfur (S). In oxygenic photosynthesis, water (H2O) serves as a substrate for photolysis resulting in the generation of diatomic oxygen (O2). 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 modelsThe 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 transfer 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 (O2) is generated and the hydrogen of the water molecules has been converted to four protons released into the thylakoid lumen. These protons, as well as additional protons pumped across the thylakoid membrane coupled with the electron transfer 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 transfer chain and finally combine with the coenzyme NADP+ and protons outside the thylakoids to NADPH. Thus, the net oxidation reaction of water photolysis can be written as: 2 H2O + 2 NADP+ + 8 photons (light) → 2 NADPH + 2 H+ + O2 The free energy change (ΔG) 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 modelsIn 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.Gregory S. Engel, Tessa R. Calhoun, Elizabeth L. Read, Tae-Kyu Ahn, Tomáš Mančal, Yuan-Chung Cheng, Robert E. Blankenship and Graham R. Fleming, "Evidence for wavelike energy transfer through quantum coherence in photosynthetic systems", in Nature 446, 782-786 (12 April 2007) According to Fleminghttp://www.physorg.com/news95605211.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 |author1 = Elisabetta Collini |author2 = Cathy Y. Wong |author3 = Krystyna E. Wilk |author4 = Paul M. G. Curmi |author5 = Paul Brumer |author6 = Gregory D. Scholes |title = Coherently wired light-harvesting in photosynthetic marine algae at ambient temperature |journal = Nature |volume = 463 |date = 4 February 2010 |doi = 10.1038/nature08811 |pmid=20130647 |bibcode = 2010Natur.463..644C |issue=7281 |pages=644–7}}
Photolysis in the atmospherePhotolysis occurs in the atmosphere as part of a series of reactions by which primary pollutants such as hydrocarbons and nitrogen oxides react to form secondary pollutants such as peroxyacyl nitrates. See photochemical smog. The two most important photodissociaton reactions in the troposphere are firstly: O3 + hν → O2 + O(1D) λ < 320 nm which generates an excited oxygen atom which can react with water to give the hydroxyl radical: O(1D) + H2O → 2 •OH The hydroxyl radical is central to atmospheric chemistry as it initiates the oxidation of hydrocarbons in the atmosphere and so acts as a detergent. Secondly the reaction: NO2 + hν → NO + O is a key reaction in the formation of tropospheric ozone. The formation of the ozone layer is also caused by photodissociation. Ozone in the Earth's stratosphere is created by ultraviolet light striking oxygen molecules containing two oxygen atoms (O2), splitting them into individual oxygen atoms (atomic oxygen). The atomic oxygen then combines with unbroken O2 to create ozone, O3. In addition, photolysis is the process by which CFCs are broken down in the upper atmosphere to form ozone-destroying chlorine free radicals.
AstrophysicsIn astrophysics, photodissociation is one of the major processes through which molecules are broken down (but new molecules are being formed). Because of the vacuum of the interstellar medium, molecules and free radicals can exist for a long time. Photodissociation is the main path by which molecules are broken down. Photodissociation rates are important in the study of the composition of interstellar clouds in which stars are formed. Examples of photodissociation in the interstellar medium are (h\nu is the energy of a single photon of frequency \nu): H_2O + h\nu \rightarrow H + OH CH_4 +h\nu \rightarrow CH_3 + H
Atmospheric gamma-ray burstsCurrently orbiting satellites detect an average of about one gamma-ray burst per day. Because gamma-ray bursts are visible to distances encompassing most of the observable universe, a volume encompassing many billions of galaxies, this suggests that gamma-ray bursts must be exceedingly rare events per galaxy. Measuring the exact rate of gamma-ray bursts is difficult, but for a galaxy of approximately the same size as the Milky Way, the expected rate (for long GRBs) is about one burst every 100,000 to 1,000,000 years. Podsiadlowski 2004 Only a few percent of these would be beamed towards Earth. Estimates of rates of short GRBs are even more uncertain because of the unknown beaming fraction, but are probably comparable. Guetta 2006 A gamma-ray burst in the Milky Way, if close enough to Earth and beamed towards it, could have significant effects on the biosphere. The absorption of radiation in the atmosphere would cause photodissociation of nitrogen, generating nitric oxide that would act as a catalyst to destroy ozone. Thorsett 1995 The atmospheric photodissociation
- N2 -> 2N
- O2 -> 2O
- CO2 -> C + 2O
- H2O -> 2H + O
- 2NH3 -> 3H2 + N2
- NO2 (consumes up to 400 ozone molecules)
- CH2 (nominal)
- CH4 (nominal)