Excimer

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Excimer energy diagram Excimer energy diagram.svg
Excimer energy diagram

An excimer (originally short for excited dimer) is a short-lived polyatomic molecule formed from two species that do not form a stable molecule in the ground state. In this case, formation of molecules is possible only if such atom is in an electronic excited state. [1] Heteronuclear molecules and molecules that have more than two species are also called exciplex molecules (originally short for excited complex). Excimers are often diatomic and are composed of two atoms or molecules that would not bond if both were in the ground state. The lifetime of an excimer is very short, on the order of nanoseconds.

Contents

Formation and decay

Molecular orbitals Molecule HOMO-LUMO diagram.svg
Molecular orbitals

Under the molecular orbital formalism, a typical ground-state molecule has electrons in the lowest possible energy levels. According to the Pauli principle, at most two electrons can occupy a given orbital, and if an orbital contains two electrons they must be in opposite spin states. The highest occupied molecular orbital is called the HOMO and the lowest unoccupied molecular orbital is called the LUMO; the energy gap between these two states is known as the HOMO–LUMO gap. If the molecule absorbs light whose energy is equal to this gap, an electron in the HOMO may be excited to the LUMO. This is called the molecule's excited state.

Excimers are only formed when one of the dimer components is in the excited state. When the excimer returns to the ground state, its components dissociate and often repel each other. The wavelength of an excimer's emission is longer (smaller energy) than that of the excited monomer's emission. An excimer can thus be measured by fluorescent emissions.

Because excimer formation is dependent on a bimolecular interaction, it is promoted by high monomer density. Low-density conditions produce excited monomers that decay to the ground state before they interact with an unexcited monomer to form an excimer.

Usage note

The term excimer (excited state dimer) is, strictly speaking, limited to cases in which a true dimer is formed; that is, both components of the dimer are the same molecule or atom. The term exciplex refers to the heterodimeric case; however, common usage expands excimer to cover this situation.

Examples and use

Excimer lasers
LaserReagentsEmission peak
XeCl Xe + Cl
2
308 nm
KrF Kr + NF
3
248 nm
ArF Ar + F
2
193 nm

Heterodimeric diatomic complexes involving a noble gas and a halide, such as xenon chloride, are common in the construction of excimer lasers, which are excimers' most common application. These lasers take advantage of the fact that excimer components have attractive interactions in the excited state and repulsive interactions in the ground state. Emission of excimer molecules is also used as a source of spontaneous ultraviolet light (excimer lamps). [2]

The molecule pyrene is another canonical example of an excimer that has found applications in biophysics to evaluate the distance between biomolecules. [3]

In organic chemistry, many reactions occur through an exciplex, for example, those of simple arene compounds with alkenes. [4] The reactions of benzene and their products depicted are a [2+2]cycloaddition to the ortho product (A), [5] a [2+3]cycloaddition to the meta product (B) [6] and the [2+4]cycloaddition to the para product (C) [7] with simple alkenes such as the isomers of 2-butene. In these reactions, it is the arene that is excited.

Arene photocycloadditions Arenephotocycloadditions.svg
Arene photocycloadditions

As a general rule, the regioselectivity is in favor of the ortho adduct at the expense of the meta adduct when the amount of charge transfer taking place in the exciplex increases.

Generation techniques

It takes a noble gas atom in an excited electronic state to form an excimer molecule such as a noble gas dimer or noble gas halide. Sufficiently high energy (approximately 10 eV) is required to obtain a noble gas atom in the lowest excited electronic state, which provides the formation of an excimer molecule. The most convenient way to excite gases is by an electric discharge. That is why such excimer molecules are generated in a plasma (see excimer molecule formation).

Fluorescence quenching

Exciplexes provide one of the three dynamic mechanisms by which fluorescence is quenched. A regular exciplex has some charge-transfer (CT) character, and in the extreme case there are distinct radical ions with unpaired electrons. If the unpaired electrons can spin-pair to form a covalent bond, then the covalent bonding interaction can lower the energy of the charge transfer state. Strong CT stabilisation has been shown to lead to a conical intersection of this exciplex state with the ground state in a balance of steric effects, electrostatic interactions, stacking interactions, and relative conformations that can determine the formation and accessibility of bonded exciplexes. [8]

As an exception to the conventional radical ion pair model, this mode of covalent bond formation is of interest to photochemistry research, as well as the many biological fields using fluorescence spectroscopy techniques. Evidence for the bonded exciplex intermediate has been given in studies of steric and Coulombic effects on the quenching rate constants and from extensive density functional theory computations that show a curve crossing between the ground state and the low-energy bonded exciplex state. [9]

See also

Related Research Articles

In chemistry, dimerization refers to the process of joining two molecular entities by bonds. The resulting bonds can be either strong or weak. Many symmetrical chemical species are described as dimers, even when the monomer is unknown or highly unstable.

<span class="mw-page-title-main">Photochemistry</span> Sub-discipline of chemistry

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, visible light (400–750 nm) or infrared radiation (750–2500 nm).

<span class="mw-page-title-main">Excited state</span> Quantum states with more energy than the lowest possible amount

In quantum mechanics, an excited state of a system is any quantum state of the system that has a higher energy than the ground state. Excitation refers to an increase in energy level above a chosen starting point, usually the ground state, but sometimes an already excited state. The temperature of a group of particles is indicative of the level of excitation.

<span class="mw-page-title-main">Excimer laser</span> Type of ultraviolet laser important in chip manufacturing and eye surgery

An excimer laser, sometimes more correctly called an exciplex laser, is a form of ultraviolet laser which is commonly used in the production of microelectronic devices, semiconductor based integrated circuits or "chips", eye surgery, and micromachining.

<span class="mw-page-title-main">Singlet oxygen</span> Oxygen with all of its electrons spin paired

Singlet oxygen, systematically named dioxygen(singlet) and dioxidene, is a gaseous inorganic chemical with the formula O=O (also written as 1
[O
2
]
or 1
O
2
), which is in a quantum state where all electrons are spin paired. It is kinetically unstable at ambient temperature, but the rate of decay is slow.

<span class="mw-page-title-main">Krypton fluoride laser</span>

A krypton fluoride laser is a particular type of excimer laser, which is sometimes called an exciplex laser. With its 248 nanometer wavelength, it is a deep ultraviolet laser which is commonly used in the production of semiconductor integrated circuits, industrial micromachining, and scientific research. The term excimer is short for 'excited dimer', while exciplex is short for 'excited complex'. An excimer laser typically contains a mixture of: a noble gas such as argon, krypton, or xenon; and a halogen gas such as fluorine or chlorine. Under suitably intense conditions of electromagnetic stimulation and pressure, the mixture emits a beam of coherent stimulated radiation as laser light in the ultraviolet range.

<span class="mw-page-title-main">Photosensitizer</span> Type of molecule reacting to light

Photosensitizers are light absorbers that alter the course of a photochemical reaction. They usually are catalysts. They can function by many mechanisms, sometimes they donate an electron to the substrate, sometimes they abstract a hydrogen atom from the substrate. At the end of this process, the photosensitizer returns to its ground state, where it remains chemically intact, poised to absorb more light. One branch of chemistry which frequently utilizes photosensitizers is polymer chemistry, using photosensitizers in reactions such as photopolymerization, photocrosslinking, and photodegradation. Photosensitizers are also used to generate prolonged excited electronic states in organic molecules with uses in photocatalysis, photon upconversion and photodynamic therapy. Generally, photosensitizers absorb electromagnetic radiation consisting of infrared radiation, visible light radiation, and ultraviolet radiation and transfer absorbed energy into neighboring molecules. This absorption of light is made possible by photosensitizers' large de-localized π-systems, which lowers the energy of HOMO and LUMO orbitals to promote photoexcitation. While many photosensitizers are organic or organometallic compounds, there are also examples of using semiconductor quantum dots as photosensitizers.

<span class="mw-page-title-main">Quenching (fluorescence)</span> Reduction of light emitted from fluorescent substances

In chemistry, quenching refers to any process which decreases the fluorescent intensity of a given substance. A variety of processes can result in quenching, such as excited state reactions, energy transfer, complex-formation and collisions. As a consequence, quenching is often heavily dependent on pressure and temperature. Molecular oxygen, iodine ions and acrylamide are common chemical quenchers. The chloride ion is a well known quencher for quinine fluorescence. Quenching poses a problem for non-instant spectroscopic methods, such as laser-induced fluorescence.

<span class="mw-page-title-main">Woodward–Hoffmann rules</span> Set of rules pertaining to pericyclic reactions

The Woodward–Hoffmann rules, devised by Robert Burns Woodward and Roald Hoffmann, are a set of rules used to rationalize or predict certain aspects of the stereochemistry and activation energy of pericyclic reactions, an important class of reactions in organic chemistry. The rules are best understood in terms of the concept of the conservation of orbital symmetry using orbital correlation diagrams. The Woodward–Hoffmann rules are a consequence of the changes in electronic structure that occur during a pericyclic reaction and are predicated on the phasing of the interacting molecular orbitals. They are applicable to all classes of pericyclic reactions, including (1) electrocyclizations, (2) cycloadditions, (3) sigmatropic reactions, (4) group transfer reactions, (5) ene reactions, (6) cheletropic reactions, and (7) dyotropic reactions. The Woodward–Hoffmann rules exemplify the power of molecular orbital theory.

<span class="mw-page-title-main">Sextuple bond</span> Covalent bond involving 12 bonding electrons

A sextuple bond is a type of covalent bond involving 12 bonding electrons and in which the bond order is 6. The only known molecules with true sextuple bonds are the diatomic dimolybdenum (Mo2) and ditungsten (W2), which exist in the gaseous phase and have boiling points of 4,639 °C (8,382 °F) and 5,930 °C (10,710 °F) respectively.

Photoelectrochemical processes are processes in photoelectrochemistry; they usually involve transforming light into other forms of energy. These processes apply to photochemistry, optically pumped lasers, sensitized solar cells, luminescence, and photochromism.

The argon fluoride laser is a particular type of excimer laser, which is sometimes called an exciplex laser. With its 193-nanometer wavelength, it is a deep ultraviolet laser, which is commonly used in the production of semiconductor integrated circuits, eye surgery, micromachining, and scientific research. "Excimer" is short for "excited dimer", while "exciplex" is short for "excited complex". An excimer laser typically uses a mixture of a noble gas and a halogen gas, which under suitable conditions of electrical stimulation and high pressure, emits coherent stimulated radiation in the ultraviolet range.

<span class="mw-page-title-main">Polyfluorene</span> Chemical compound

Polyfluorene is a polymer with formula (C13H8)n, consisting of fluorene units linked in a linear chain — specifically, at carbon atoms 2 and 7 in the standard fluorene numbering. It can also be described as a chain of benzene rings linked in para positions with an extra methylene bridge connecting every pair of rings.

Xenon monochloride (XeCl) is an exciplex which is used in excimer lasers and excimer lamps emitting near ultraviolet light at 308 nm. It is most commonly used in medicine. Xenon monochloride was first synthesized in the 1960s. Its kinetic scheme is very complex and its state changes occur on a nanosecond timescale. In the gaseous state, at least two kinds of xenon monochloride are known: XeCl and Xe
2
Cl
, whereas complex aggregates form in the solid state in noble gas matrices. The excited state of xenon resembles halogens and it reacts with them to form excited molecular compounds.

An excimer lamp is a source of ultraviolet light based on spontaneous emission of excimer (exciplex) molecules.

<span class="mw-page-title-main">Photoredox catalysis</span>

Photoredox catalysis is a branch of photochemistry that uses single-electron transfer. Photoredox catalysts are generally drawn from three classes of materials: transition-metal complexes, organic dyes, and semiconductors. While organic photoredox catalysts were dominant throughout the 1990s and early 2000s, soluble transition-metal complexes are more commonly used today.

<span class="mw-page-title-main">Helium dimer</span> Chemical compound

The helium dimer is a van der Waals molecule with formula He2 consisting of two helium atoms. This chemical is the largest diatomic molecule—a molecule consisting of two atoms bonded together. The bond that holds this dimer together is so weak that it will break if the molecule rotates, or vibrates too much. It can only exist at very low cryogenic temperatures.

The [4+4] Photocycloaddition is a cycloaddition reaction in which two unsaturated molecules connect via four atoms from each molecule to create an eight-membered ring. As a photochemical reaction, it is promoted by some form of light, as opposed to a thermal process.

Neon compounds are chemical compounds containing the element neon (Ne) with other molecules or elements from the periodic table. Compounds of the noble gas neon were believed not to exist, but there are now known to be molecular ions containing neon, as well as temporary excited neon-containing molecules called excimers. Several neutral neon molecules have also been predicted to be stable, but are yet to be discovered in nature. Neon has been shown to crystallize with other substances and form clathrates or Van der Waals solids.

Second-order Jahn-Teller distortion is a singular, general, and powerful approach rigorously based in first-principle vibronic coupling interactions. It enables prediction and explication of molecular geometries that are not necessarily satisfactorily or even correctly explained by semi-empirical theories such as Walsh diagrams, atomic state hybridization, valence shell electron pair repulsion (VSEPR), softness-hardness-based models, aromaticity and antiaromaticity, hyperconjugation, etc.

References

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  8. Liang, JingXin; Nguyen, Quynh L.; Matsika, Spiridoula (2013). "Exciplexes and conical intersections lead to fluorescence quenching in π-stacked dimers of 2-aminopurine with natural purine nucleobases". Photochemical & Photobiological Sciences. 12 (8): 1387–1400. doi:10.1039/c3pp25449f. ISSN   1474-905X. PMC   5006741 . PMID   23625036.
  9. Wang, Yingsheng; Haze, Olesya; Dinnocenzo, Joseph P.; Farid, Samir; Farid, Ramy S.; Gould, Ian R. (2007). "Bonded Exciplexes. A New Concept in Photochemical Reactions". The Journal of Organic Chemistry. 72 (18): 6970–6981. doi:10.1021/jo071157d. ISSN   0022-3263. PMID   17676917.