Photochemistry

Photochemistry is the branch of chemistry concerned with the chemical effects of light. Generally, this term is used to describe a chemical reaction caused by absorption of ultraviolet (wavelength from 100 to 400 nm), visible light (400–750 nm) or infrared radiation (750–2500 nm). Photochemistry is the branch of chemistry concerned with the chemical effects of light. Generally, this term is used to describe a chemical reaction caused by absorption of ultraviolet (wavelength from 100 to 400 nm), visible light (400–750 nm) or infrared radiation (750–2500 nm). In nature, photochemistry is of immense importance as it is the basis of photosynthesis, vision, and the formation of vitamin D with sunlight. Photochemical reactions proceed differently than temperature-driven reactions. Photochemical paths access high energy intermediates that cannot be generated thermally, thereby overcoming large activation barriers in a short period of time, and allowing reactions otherwise inaccessible by thermal processes. Photochemistry is also destructive, as illustrated by the photodegradation of plastics. Photoexcitation is the first step in a photochemical process where the reactant is elevated to a state of higher energy, an excited state. The first law of photochemistry, known as the Grotthuss–Draper law (for chemists Theodor Grotthuss and John W. Draper), states that light must be absorbed by a chemical substance in order for a photochemical reaction to take place. According to the second law of photochemistry, known as the Stark-Einstein law (for physicists Johannes Stark and Albert Einstein), for each photon of light absorbed by a chemical system, no more than one molecule is activated for a photochemical reaction, as defined by the quantum yield. When a molecule or atom in the ground state (S0) absorbs light, one electron is excited to a higher orbital level. This electron maintains its spin according to the spin selection rule; other transitions would violate the law of conservation of angular momentum.The excitation to a higher singlet state can be from HOMO to LUMO or to a higher orbital, so that singlet excitation states S1, S2, S3… at different energies are possible. Kasha's rule stipulates that higher singlet states would quickly relax by radiationless decay or internal conversion (IC) to S1. Thus, S1 is usually, but not always, the only relevant singlet excited state. This excited state S1 can further relax to S0 by IC, but also by an allowed radiative transition from S1 to S0 that emits a photon; this process is called fluorescence. Alternatively, it is possible for the excited state S1 to undergo spin inversion and to generate a triplet excited state T1 having two unpaired electrons with the same spin. This violation of the spin selection rule is possible by intersystem crossing (ISC) of the vibrational and electronic levels of S1 and T1. According to Hund's rule of maximum multiplicity, this T1 state would be somewhat more stable than S1. This triplet state can relax to the ground state S0 by radiationless IC or by a radiation pathway called phosphorescence. This process implies a change of electronic spin, which is forbidden by spin selection rules, making phosphorescence (from T1 to S0) much slower than fluorescence (from S1 to S0). Thus, triplet states generally have longer lifetimes than singlet states. These transitions are usually summarized in a state energy diagram or Jablonski diagram, the paradigm of molecular photochemistry. These excited species, either S1 or T1, have a half empty low-energy orbital, and are consequently more oxidizing than the ground state. But at the same time, they have an electron in a high energy orbital, and are thus more reducing. In general, excited species are prone to participate in electron transfer processes. Photochemical reactions require a light source that emits wavelengths corresponding to an electronic transition in the reactant. In the early experiments (and in everyday life), sunlight was the light source, although it is polychromatic. Mercury-vapor lamps are more common in the laboratory. Low pressure mercury vapor lamps mainly emit at 254 nm. For polychromatic sources, wavelength ranges can be selected using filters. Alternatively, laser beams are usually monochromatic (although two or more wavelengths can be obtained using nonlinear optics) and LEDs have a relatively narrowband that can be efficiently used, as well as Rayonet lamps, to get approximately monochromatic beams.