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Fluorescence is the emission of
light by a substance that has absorbed light or other
electromagnetic radiation. It is a form of
luminescence. In most cases, the emitted light has a longer
wavelength, and therefore a lower
photon energy, than the absorbed radiation. A perceptible example of fluorescence occurs when the absorbed radiation is 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 that can only be seen when the substance has been exposed to
UV light. Fluorescent materials cease to glow nearly immediately when the radiation source stops, unlike
phosphorescent materials, which continue to emit light for some time after.
Fluorescence has many practical applications, including
mineralogy
Mineralogy is a subject of geology specializing in the scientific study of the chemistry, crystal structure, and physical (including optical) properties of minerals and mineralized artifacts. Specific studies within mineralogy include the proces ...
,
gemology,
medicine, chemical sensors (
fluorescence spectroscopy),
fluorescent labelling,
dye
A dye is a colored substance that chemically bonds to the substrate to which it is being applied. This distinguishes dyes from pigments which do not chemically bind to the material they color. Dye is generally applied in an aqueous solution an ...
s, biological detectors, cosmic-ray detection,
vacuum fluorescent displays, and
cathode-ray tube
A cathode-ray tube (CRT) is a vacuum tube containing one or more electron guns, which emit electron beams that are manipulated to display images on a phosphorescent screen. The images may represent electrical waveforms (oscilloscope), pictur ...
s. Its most common everyday application is in (
gas-discharge)
fluorescent lamps and
LED lamps
An LED lamp or LED light bulb is an electric light that produces light using light-emitting diodes (LEDs). LED lamps are significantly more energy-efficient than equivalent incandescent lamps
and can be significantly more efficient than mos ...
, in which fluorescent coatings convert UV or blue light into longer-wavelengths resulting in
white light
White is the lightest color and is achromatic (having no hue). It is the color of objects such as snow, chalk, and milk, and is the opposite of black. White objects fully reflect and scatter all the visible wavelengths of light. White on ...
which can even appear indistinguishable from that of the traditional but energy- inefficient
incandescent lamp
An incandescent light bulb, incandescent lamp or incandescent light globe is an electric light with a wire filament heated until it glows. The filament is enclosed in a glass bulb with a vacuum or inert gas to protect the filament from oxid ...
.
Fluorescence also occurs frequently in nature in some minerals and in many biological forms across all kingdoms of life. The latter may be referred to as ''biofluorescence'', indicating that the
fluorophore is part of or is extracted from a living organism (rather than an inorganic
dye
A dye is a colored substance that chemically bonds to the substrate to which it is being applied. This distinguishes dyes from pigments which do not chemically bind to the material they color. Dye is generally applied in an aqueous solution an ...
or
stain
A stain is a discoloration that can be clearly distinguished from the surface, material, or medium it is found upon. They are caused by the chemical or physical interaction of two dissimilar materials. Accidental staining may make materials app ...
). But since fluorescence is due to a specific chemical, which can also be synthesized artificially in most cases, it is sufficient to describe the substance itself as ''fluorescent''.
History
An early observation of fluorescence was 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''.
[
][
]
The chemical compound responsible for this fluorescence is matlaline, which is the oxidation product of one of the
flavonoid
Flavonoids (or bioflavonoids; from the Latin word ''flavus'', meaning yellow, their color in nature) are a class of polyphenolic secondary metabolites found in plants, and thus commonly consumed in the diets of humans.
Chemically, flavonoids ...
s found in this wood.
[
In 1819, E.D. Clarke
and in 1822 René Just Haüy
described fluorescence in fluorites, Sir David Brewster described the phenomenon for ]chlorophyll
Chlorophyll (also chlorophyl) is any of several related green pigments found in cyanobacteria and in the chloroplasts of algae and plants. Its name is derived from the Greek words , ("pale green") and , ("leaf"). Chlorophyll allow plants to a ...
in 1833
and Sir John Herschel did the same for quinine in 1845.
In his 1852 paper on the "Refrangibility" ( wavelength change) of light, George Gabriel Stokes described the ability of fluorspar
Fluorite (also called fluorspar) is the mineral form of calcium fluoride, CaF2. It belongs to the halide minerals. It crystallizes in isometric cubic habit, although octahedral and more complex isometric forms are not uncommon.
The Mohs scal ...
and uranium glass to change invisible light beyond the violet end of the visible spectrum into blue light. He named this phenomenon ''fluorescence''
: "I am almost inclined to coin a word, and call the appearance ''fluorescence'', from fluor-spar .e., fluorite as the analogous term ''opalescence'' is derived from the name of a mineral."[
]
The name was derived from the mineral fluorite (calcium difluoride), some examples of which contain traces of divalent europium
Europium is a chemical element with the symbol Eu and atomic number 63. Europium is the most reactive lanthanide by far, having to be stored under an inert fluid to protect it from atmospheric oxygen or moisture. Europium is also the softest lanth ...
, which serves as the fluorescent activator to emit blue light. In a key experiment he used a prism to isolate ultraviolet radiation from sunlight and observed blue light emitted by an ethanol solution of quinine exposed by it.
Physical principles
Mechanism
Fluorescence occurs when an excited molecule, atom, or nanostructure, relaxes to a lower energy state (usually the ground state
The ground state of a quantum-mechanical system is its stationary state of lowest energy; the energy of the ground state is known as the zero-point energy of the system. An excited state is any state with energy greater than the ground state. ...
) through emission of a photon without a change in electron spin. When the initial and final states have different multiplicity (spin), the phenomenon is termed phosphorescence.
The ground state of most molecules is a singlet state, denoted as S0. A notable exception is molecular oxygen, which has a triplet
A triplet is a set of three items, which may be in a specific order, or unordered. It may refer to:
Science
* A series of three nucleotide bases forming an element of the Genetic code
* J-coupling as part of Nuclear magnetic resonance spectrosc ...
ground state. Absorption of a photon of energy results in an excited state of the same multiplicity (spin) of the ground state, usually a singlet (Sn with n > 0). In solution, states with n > 1 relax rapidly to the lowest vibrational level of the first excited state (S1) 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. Therefore, most commonly, fluorescence occurs from the first singlet excited state, S1. Fluorescence is the emission of a photon accompanying the relaxation of the excited state to the ground state. Fluorescence photons are lower in energy () compared to the energy of the photons used to generate the excited state ()
* Excitation:
* Fluorescence (emission):
In each case the photon energy is proportional to its frequency according to , where is Planck's constant.
The excited state S1 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. 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 (O2) is an extremely efficient quencher of fluorescence just because of its unusual triplet ground state.
Quantum yield
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.[
]
:
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:
:
where is the rate constant of spontaneous emission
Spontaneous emission is the process in which a quantum mechanical system (such as a molecule, an atom or a subatomic particle) transits from an excited energy state to a lower energy state (e.g., its ground state) and emits a quantized amount of ...
of radiation and
:
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
Resonance describes the phenomenon of increased amplitude that occurs when the frequency of an applied Periodic function, periodic force (or a Fourier analysis, Fourier component of it) is equal or close to a natural frequency of the system ...
)
* 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. The quinine salt ''quinine sulfate'' in a sulfuric acid
Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid ( Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular formu ...
solution was regarded as the most common fluorescence standard,
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.
Lifetime
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:
:
where