Electride 01
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An electride is an
ionic compound In chemistry, a salt or ionic compound is a chemical compound consisting of an assembly of positively charged ions (Cation, cations) and negatively charged ions (Anion, anions), which results in a compound with no net electric charge (electrica ...
in which an
electron The electron (, or in nuclear reactions) is a subatomic particle with a negative one elementary charge, elementary electric charge. It is a fundamental particle that comprises the ordinary matter that makes up the universe, along with up qua ...
serves the role of the
anion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conven ...
.


Solutions

Solutions of
alkali metal The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K),The symbols Na and K for sodium and potassium are derived from their Latin names, ''natrium'' and ''kalium''; these are still the origins of the names ...
s in
ammonia Ammonia is an inorganic chemical compound of nitrogen and hydrogen with the chemical formula, formula . A Binary compounds of hydrogen, stable binary hydride and the simplest pnictogen hydride, ammonia is a colourless gas with a distinctive pu ...
are electride salts. In the case of sodium, these blue
solution Solution may refer to: * Solution (chemistry), a mixture where one substance is dissolved in another * Solution (equation), in mathematics ** Numerical solution, in numerical analysis, approximate solutions within specified error bounds * Solu ...
s consist of a(NH3)6sup>+ and solvated electrons: :Na + 6 NH3a(NH3)6sup>+ + e The cation a(NH3)6sup>+ is an
octahedral In geometry, an octahedron (: octahedra or octahedrons) is any polyhedron with eight faces. One special case is the regular octahedron, a Platonic solid composed of eight equilateral triangles, four of which meet at each vertex. Many types of i ...
coordination complex A coordination complex is a chemical compound consisting of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a surrounding array of chemical bond, bound molecules or ions, that are in turn known as ' ...
. Despite the name, the electron does not leave the sodium-ammonia complex, but it is transferred from Na to the vacant orbitals of the coordinated ammonia molecules. Similar solutions exist in
hexamethylphosphoramide Hexamethylphosphoramide, often abbreviated HMPA, is a phosphoramide (an amide of phosphoric acid) with the formula This colorless liquid is used as a solvent in organic synthesis. Structure and reactivity HMPA is the oxide of tris(dimethyla ...
.


Solid salts

Many "inorganic electrides" have been described. Addition of a complexant like
crown ether In organic chemistry, crown ethers are cyclic chemical compounds that consist of a ring containing several ether groups (). The most common crown ethers are cyclic oligomers of ethylene oxide, the repeating unit being ethyleneoxy, i.e., . Impor ...
or .2.2cryptand to a solution of a(NH3)6sup>+e affords a (crown ether)sup>+e or a(2,2,2-crypt)sup>+e. Evaporation of these solutions yields a blue-black paramagnetic solid with the formula a(2,2,2-crypt)sup>+e. Most solid electride salts decompose above 240 K, although a24Al28O64sup>4+(e)4 is stable at room temperature. In these salts, the electron is delocalized between the
cation An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convent ...
s. Properties of these salts have been analyzed. ThI2 and ThI3 have also been proposed to be electride compounds. Similarly, , , , and are
all All or ALL may refer to: عرص Biology and medicine * Acute lymphoblastic leukemia, a cancer * Anterolateral ligament, a ligament in the knee * ''All.'', taxonomic author abbreviation for Carlo Allioni (1728–1804), Italian physician and pro ...
electride salts with a tricationic metal ion.


Organometallic electrides

Magnesium reduced nickel(II)-bipyridyl (bipy) complex have been labeled organic electrides. An example is THF)4Mg42-bipy)4sup>–, in which the electride is the singly occupied molecular orbital (SOMO) formed by the Mg-square cluster within the larger complex.


Reactions

Electride salts are powerful
reducing agent In chemistry, a reducing agent (also known as a reductant, reducer, or electron donor) is a chemical species that "donates" an electron to an (called the , , , or ). Examples of substances that are common reducing agents include hydrogen, carbon ...
s, as demonstrated by their use in the
Birch reduction The Birch reduction or Metal-Ammonia reduction is an organic reaction that is used to convert arenes to Cyclohexa-1,4-diene, 1,4-cyclohexadienes. The reaction is named after the Australian chemist Arthur Birch (organic chemist), Arthur Birch and i ...
. Evaporation of these blue solutions affords a mirror of Na metal. If not evaporated, such solutions slowly lose their colour as the electrons reduce ammonia: :2 a(NH3)6sup>+e → 2 NaNH2 + 10NH3 + H2 This conversion is catalyzed by various metals. An electride, a(NH3)6sup>+e, is formed as a
reaction intermediate In chemistry, a reaction intermediate, or intermediate, is a molecular entity arising within the sequence of a stepwise chemical reaction. It is formed as the reaction product of an elementary step, from the reactants and/or preceding interme ...
.


High-pressure elements

In
quantum chemistry Quantum chemistry, also called molecular quantum mechanics, is a branch of physical chemistry focused on the application of quantum mechanics to chemical systems, particularly towards the quantum-mechanical calculation of electronic contributions ...
, an electride is identified by a maximum of the electron density, characterized by a non-nuclear attractor, a large and negative Laplacian at the critical point, and an
Electron Localization Function In quantum chemistry, the electron localization function (ELF) is a measure of the likelihood of finding an electron in the neighborhood space of a reference electron located at a given point and with the same Spin (physics), spin. Physically, th ...
isosurface close to 1. Electride phases are typically semiconducting or have very low conductivity, usually with a complex optical response. A sodium compound called disodium helide has been created under of pressure. It has been proven that the localized electron density in high-pressure electrides does not correspond to isolated electrons, but that it is generated by the formation of (multicenter) chemical bonds. The intrinsic
polarization Polarization or polarisation may refer to: Mathematics *Polarization of an Abelian variety, in the mathematics of complex manifolds *Polarization of an algebraic form, a technique for expressing a homogeneous polynomial in a simpler fashion by ...
between atomic nucleus and the electron anion in these high pressure electrides can lead to unique properties, such as the splitting of the longitudinal and transverse acoustic modes (''i.e.'', LA-TA splitting, an analogue to the LO-TO splitting in
ionic compound In chemistry, a salt or ionic compound is a chemical compound consisting of an assembly of positively charged ions (Cation, cations) and negatively charged ions (Anion, anions), which results in a compound with no net electric charge (electrica ...
), the universal but robust gapless surface state in insulating electride that forming a ''de facto'' real space topological distribution of charge carriers, and the colossal charge state of some impurities in them.


Layered electrides (Electrenes)

Layered electrides or electrenes are
single-layer materials In materials science, the term single-layer materials or 2D materials refers to crystalline solids consisting of a single layer of atoms. These materials are promising for some applications but remain the focus of research. Single-layer materials ...
consisting of alternating atomically thin two-dimensional layers of electrons and ionized atoms. The first example was Ca2N, in which the charge (+4) of two calcium ions is balanced by the charge of a nitride ion (−3) in the ion layer plus a charge (−1) in the electron layer.


See also

*
F-center An F-center or color center or Farbe center (from the original German ''Farbzentrum'', where ''Farbe'' means ''color'' and ''zentrum'' means ''center'') is a type of crystallographic defect in which an anionic Vacancy defect, vacancy in a crystal ...


References


Further reading

* *{{cite journal , doi=10.1021/acs.jctc.5b00993 , title=Quantifying Electron Delocalization in Electrides , date=2016 , last1=Janesko , first1=Benjamin G. , last2=Scalmani , first2=Giovanni , last3=Frisch , first3=Michael J. , journal=Journal of Chemical Theory and Computation , volume=12 , issue=1 , pages=79–91 , pmid=26652208 Salts Electron