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6 9 optical brighteners 7 see also 8 references 9 further reading 10 external links toggle the table of contents fluorescence 67 languages afrikaans العربية asturianu беларуская тарашкевіца беларуская български বাংলা bosanski català čeština dansk deutsch ελληνικά esperanto español eesti euskara فارسی suomi français gaeilge galego עברית हिन्दी hrvatski magyar հայերեն bahasa indonesia italiano 日本語 ქართული gĩkũyũ қазақша 한국어 кыргызча latina lietuvių latviešu македонски മലയാളം bahasa melayu nederlands norsk nynorsk norsk bokmål occitan polski piemontèis português română русский srpskohrvatski српскохрватски simple english slovenčina shqip српски srpski svenska தமிழ் ไทย türkçe українська اردو oʻzbekcha ўзбекча tiếng việt 吴语 ייִדיש 粵語 中文 edit links article talk english read edit view history tools tools move to sidebar hide actions read edit view history general what links here related changes upload file permanent link page information cite this page get shortened url switch to legacy parser print export download as pdf printable version in other projects wikimedia commons wikidata item appearance move to sidebar hide from wikipedia the free encyclopedia emission of light by a substance that has absorbed light not to be confused with inflorescence for the album by asobi seksu see fluorescence album fluorescent minerals emit visible light when exposed to ultraviolet fluorescent marine organisms fluorescent clothes used in black light theatre production prague fluorescence is one of two kinds of photoluminescence the emission of light by a substance that has absorbed light or other electromagnetic radiation when exposed to ultraviolet radiation many substances will glow fluoresce with colored visible light the color of the light emitted depends on the chemical composition of the substance fluorescent materials generally cease to glow nearly immediately when the radiation source stops this distinguishes them from the other type of light emission phosphorescence phosphorescent materials continue to emit light for some time after the radiation stops this difference in duration is a result of quantum spin effects fluorescence occurs when a photon from incoming radiation is absorbed by a molecule exciting it to a higher energy level followed by the emission of light as the molecule returns to a lower energy state the emitted light may have a longer wavelength and therefore a lower photon energy than the absorbed radiation for example the absorbed radiation could be in the ultraviolet region of the electromagnetic spectrum invisible to the human eye while the emitted light is in the visible region this gives the fluorescent substance a distinct color best seen when exposed to uv light making it appear to glow in the dark however any light with a shorter wavelength may cause a material to fluoresce at a longer wavelength fluorescent materials may also be excited by certain wavelengths of visible light which can mask the glow yet their colors may appear bright and intensified other fluorescent materials emit their light in the infrared or even the ultraviolet regions of the spectrum fluorescence has many practical applications including mineralogy gemology medicine chemical sensors fluorescence spectroscopy fluorescent labelling dyes biological detectors cosmic ray detection vacuum fluorescent displays and cathode ray tubes its most common everyday application is in gas discharge fluorescent lamps and led lamps where fluorescent coatings convert uv or blue light into longer wavelengths resulting in white light which can appear indistinguishable from that of the traditional but energy inefficient incandescent lamp fluorescence also occurs frequently in nature appearing in some minerals and many biological forms across all kingdoms of life the latter is often referred to as biofluorescence indicating that the fluorophore is part of or derived from a living organism rather than an inorganic dye or stain however since fluorescence results from a specific chemical property that can often be synthesized artificially it is generally sufficient to describe the substance itself as fluorescent history edit see also physical crystallography before x rays luminescence fluorescence and phosphorescence a cup made from the wood of the narra tree pterocarpus indicus beside a flask containing its fluorescent solution lignum nephriticum matlaline the fluorescent substance in the wood of the tree eysenhardtia polystachya organic compounds often with multiple ring structures that can absorb and re emit light at a longer wavelength the approximate wavelength of emission of these common dyes is shown in the color of the drawing fluorescence was observed long before it was named and understood 1 an early observation of fluorescence was known to the aztecs 1 and described in 1560 by bernardino de sahagún and in 1565 by nicolás monardes in the infusion known as lignum nephriticum latin for kidney wood it was derived from the wood of two tree species pterocarpus indicus and eysenhardtia polystachya 2 3 4 the chemical compound responsible for this fluorescence is matlaline which is the oxidation product of one of the flavonoids found in this wood 2 in 1819 e d clarke 5 and in 1822 rené just haüy 6 described some varieties of fluorites that had a different color depending on whether the light was reflected or apparently transmitted haüy incorrectly viewed the effect as light scattering similar to opalescence 1 fig 5 in 1833 sir david brewster described a similar effect in chlorophyll which he also considered a form of opalescence 7 sir john herschel studied quinine in 1845 8 9 and came to a different incorrect conclusion 1 in 1842 a e becquerel observed that calcium sulfide emits light after being exposed to solar ultraviolet making him the first to state that the emitted light is of longer wavelength than the incident light while his observation of photoluminescence was similar to that described 10 years later by stokes who observed a fluorescence of a solution of quinine the phenomenon that becquerel described with calcium sulfide is now called phosphorescence 1 in his 1852 paper on the refrangibility wavelength change of light george gabriel stokes described the ability of fluorspar uranium glass and many other substances to change invisible light beyond the violet end of the visible spectrum into visible light he named this phenomenon fluorescence 1 i am almost inclined to coin a word and call the appearance fluorescence from fluor spar i e fluorite as the analogous term opalescence is derived from the name of a mineral 10 p479 footnote neither becquerel nor stokes understood one key aspect of photoluminescence the critical difference from incandescence the emission of light by heated material to distinguish it from incandescence in the late 1800s gustav wiedemann proposed the term luminescence to designate any emission of light more intense than expected from the source s temperature 1 advances in spectroscopy and quantum electronics between the 1950s and 1970s provided a way to distinguish between the three different mechanisms that produce the light as well as narrowing down the typical timescales those mechanisms take to decay after absorption in modern science this distinction became important because some items such as lasers required the fastest decay times which typically occur in the nanosecond billionth of a second range in physics this first mechanism was termed fluorescence or singlet emission and is common in many laser mediums such as ruby other fluorescent materials were discovered to have much longer decay times because some of the atoms would change their spin to a triplet state thus would glow brightly with fluorescence under excitation but produce a dimmer afterglow for a short time after the excitation was removed which became labeled phosphorescence or triplet phosphorescence the typical decay times ranged from a few microseconds to one second which are still fast enough by human eye standards to be colloquially referred to as fluorescent common examples include fluorescent lamps organic dyes and even fluorspar longer emitters commonly referred to as glow in the dark substances ranged from one second to many hours and this mechanism was called persistent phosphorescence or persistent luminescence to distinguish it from the other two mechanisms 11 1 25 physical principles edit mechanism edit a ruby ball lens atop a green laser pointer the green beam converges into a cone within the crystal and is focused to a point on top the green light is absorbed and spontaneously remitted as red light not all of the light is absorbed and a small portion of the 520 nm laser light transmits through the top unaltered by the ruby s red color when an excited molecule atom or nanostructure emits a photon and the lower energy state usually the ground state has the same electronic spin multiplicity as the excited state the process is called fluorescence when the initial and final states have different multiplicity spin the phenomenon is termed phosphorescence 12 when a molecule in its ground state called s 0 is photoexcited it may end up in any one of a number of excited electronic states s 1 s 2 s 3 it can occupy different vibrational states within the electronic state these vibrational states are populated in proportion to their overlap with the ground state according to the franck condon principle 13 31 these vibrational excited states typically decay rapidly to the ground vibrational state of the excited electronic state s 1 followed by radiative transition to the ground state or to vibrational states close to the ground state this transition is called fluorescence all of these states are singlet states 14 225 a different pathway for deexcitation is intersystem crossing from the s 1 to a triplet state t 1 decay from t 1 to s 0 is typically slower and less intense and is called phosphorescence 14 225 absorption of a photon of energy h ν e x displaystyle h nu _ ex results in an excited state of the same multiplicity spin of the ground state usually a singlet s n with n 0 in solution states with n 1 relax rapidly to the lowest vibrational level of the first excited state s 1 by transferring energy to the solvent molecules through non radiative processes including internal conversion followed by vibrational relaxation in which the energy is dissipated as heat thus the fluorescence energy is typically less than the photoexcitation energy 13 38 the excited state s 1 can relax by other mechanisms that do not involve the emission of light these processes called non radiative processes compete with fluorescence emission and decrease its efficiency 13 examples include internal conversion intersystem crossing to the triplet state and energy transfer to another molecule an example of energy transfer is förster resonance energy transfer relaxation from an excited state can also occur through collisional quenching a process where a molecule the quencher collides with the fluorescent molecule during its excited state lifetime molecular oxygen o 2 is an extremely efficient quencher of fluorescence because of its unusual triplet ground state quantum yield edit the fluorescence quantum yield gives the efficiency of the fluorescence process it is defined as the ratio of the number of photons emitted to the number of photons absorbed 15 p10 13 φ number of photons emitted number of photons absorbed displaystyle phi frac text number of photons emitted text number of photons absorbed the maximum possible fluorescence quantum yield is 1 0 100 each photon absorbed results in a photon emitted compounds with quantum yields of 0 10 are still considered quite fluorescent another way to define the quantum yield of fluorescence is by the rate of excited state decay φ k f i k i displaystyle phi frac k _ f sum _ i k _ i where k f displaystyle k _ f is the rate constant of spontaneous emission of radiation and i k i displaystyle sum _ i k _ i is the sum of all rates of excited state decay other rates of excited state decay are caused by mechanisms other than photon emission and are therefore often called non radiative rates which can include dynamic collisional quenching near field dipole dipole interaction or resonance energy transfer internal conversion intersystem crossing thus if the rate of any pathway changes both the excited state lifetime and the fluorescence quantum yield will be affected fluorescence quantum yields are measured by comparison to a standard 16 the quinine salt quinine sulfate in a sulfuric acid solution was regarded as the most common fluorescence standard 17 however a recent study revealed that the fluorescence quantum yield of this solution is strongly affected by the temperature and should no longer be used as the standard solution the quinine in 0 1 m perchloric acid φ 0 60 shows no temperature dependence up to 45 c therefore it can be considered as a reliable standard solution 18 lifetime edit jablonski diagram after an electron absorbs a high energy photon the system is excited electronically and vibrationally the system relaxes vibrationally and eventually fluoresces at a longer wavelength than the original high energy photon had the fluorescence lifetime refers to the average time the molecule stays in its excited state before emitting a photon fluorescence typically follows first order kinetics s 1 s 1 0 e γ t displaystyle left s_ 1 right left s_ 1 right _ 0 e gamma t where s 1 displaystyle left s_ 1 right is the concentration of excited state molecules at time t displaystyle t s 1 0 displaystyle left s_ 1 right _ 0 is the initial concentration and γ displaystyle gamma is the decay rate or the inverse of the fluorescence lifetime this is an instance of exponential decay various radiative and non radiative processes can de populate the excited state in such case the total decay rate is the sum over all rates γ t o t γ r a d γ n r a d displaystyle gamma _ tot gamma _ rad gamma _ nrad where γ t o t displaystyle gamma _ tot is the total decay rate γ r a d displaystyle gamma _ rad the radiative decay rate and γ n r a d displaystyle gamma _ nrad the non radiative decay rate it is similar to a first order chemical reaction in which the first order rate constant is the sum of all of the rates a parallel kinetic model if the rate of spontaneous emission or any of the other rates are fast the lifetime is short for commonly used fluorescent compounds typical excited state decay times for photon emissions with energies from the uv to near infrared are within the range of 0 5 to 20 nanoseconds the fluorescence lifetime is an important parameter for practical applications of fluorescence such as fluorescence resonance energy transfer and fluorescence lifetime imaging microscopy jablonski diagram edit the jablonski diagram describes most of the relaxation mechanisms for excited state molecules the diagram alongside shows how fluorescence occurs due to the rel...
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