In
chemistry, delocalized electrons are
electron
The electron ( or ) is a subatomic particle with a negative one elementary electric charge. Electrons belong to the first generation of the lepton particle family,
and are generally thought to be elementary particles because they have no kno ...
s in a
molecule
A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and bioch ...
,
ion
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 conv ...
or solid
metal
A metal (from Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. Metals are typica ...
that are not associated with a single
atom or a
covalent bond
A covalent bond is a chemical bond that involves the sharing of electrons to form electron pairs between atoms. These electron pairs are known as shared pairs or bonding pairs. The stable balance of attractive and repulsive forces between atom ...
.
[IUPAC Gold Boo]
''delocalization''
/ref>
The term delocalization is general and can have slightly different meanings in different fields:
* In organic chemistry
Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms that contain carbon atoms.Clayden, J.; ...
, it refers to resonance
Resonance describes the phenomenon of increased amplitude that occurs when the frequency of an applied periodic force (or a Fourier component of it) is equal or close to a natural frequency of the system on which it acts. When an oscillati ...
in conjugated system
In theoretical chemistry, a conjugated system is a system of connected p-orbitals with delocalized electrons in a molecule, which in general lowers the overall energy of the molecule and increases stability. It is conventionally represented a ...
s and aromatic compounds
Aromatic compounds, also known as "mono- and polycyclic aromatic hydrocarbons", are organic compounds containing one or more aromatic rings. The parent member of aromatic compounds is benzene. The word "aromatic" originates from the past grouping ...
.
* In solid-state physics
Solid-state physics is the study of rigid matter, or solids, through methods such as quantum mechanics, crystallography, electromagnetism, and metallurgy. It is the largest branch of condensed matter physics. Solid-state physics studies how the ...
, it refers to free electrons that facilitate electrical conduction
Electrical resistivity (also called specific electrical resistance or volume resistivity) is a fundamental property of a material that measures how strongly it resists electric current. A low resistivity indicates a material that readily allows ...
.
* 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 ...
, it refers to molecular orbital
In chemistry, a molecular orbital is a mathematical function describing the location and wave-like behavior of an electron in a molecule. This function can be used to calculate chemical and physical properties such as the probability of findin ...
electrons that have extended over several adjacent atoms.
Resonance
In the simple aromatic ring
Simple aromatic rings, also known as simple arenes or simple aromatics, are aromatic organic compounds that consist only of a conjugated planar ring system. Many simple aromatic rings have trivial names. They are usually found as substructures of ...
of benzene
Benzene is an organic chemical compound with the molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar ring with one hydrogen atom attached to each. Because it contains only carbon and hydrogen atoms ...
, the delocalization of six π electrons over the C6 ring is often graphically indicated by a circle. The fact that the six C-C bonds are equidistant is one indication that the electrons are delocalized; if the structure were to have isolated double bonds alternating with discrete single bonds, the bond would likewise have alternating longer and shorter lengths. In valence bond theory
In chemistry, valence bond (VB) theory is one of the two basic theories, along with molecular orbital (MO) theory, that were developed to use the methods of quantum mechanics to explain chemical bonding. It focuses on how the atomic orbitals of ...
, delocalization in benzene is represented by resonance structures
In chemistry, resonance, also called mesomerism, is a way of describing bonding in certain molecules or polyatomic ions by the combination of several contributing structures (or ''forms'', also variously known as ''resonance structures'' or ' ...
.
Electrical conduction
Delocalized electrons also exist in the structure of solid metals. Metallic structure consists of aligned positive ion
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 conv ...
s (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 conven ...
s) in a "sea" of delocalized electrons. This means that the electrons are free to move throughout the structure, and gives rise to properties such as conductivity
Conductivity may refer to:
*Electrical conductivity, a measure of a material's ability to conduct an electric current
**Conductivity (electrolytic), the electrical conductivity of an electrolyte in solution
**Ionic conductivity (solid state), elec ...
.
In diamond
Diamond is a solid form of the element carbon with its atoms arranged in a crystal structure called diamond cubic. Another solid form of carbon known as graphite is the chemically stable form of carbon at room temperature and pressure, ...
all four outer electrons of each carbon atom are 'localized' between the atoms in covalent bonding. The movement of electrons is restricted and diamond does not conduct an electric current. In graphite
Graphite () is a crystalline form of the element carbon. It consists of stacked layers of graphene. Graphite occurs naturally and is the most stable form of carbon under standard conditions. Synthetic and natural graphite are consumed on lar ...
, each carbon atom uses only 3 of its 4 outer energy level electrons in covalently bonding to three other carbon atoms in a plane. Each carbon atom contributes one electron to a delocalized system of electrons that is also a part of the chemical bonding. The delocalized electrons are free to move throughout the plane. For this reason, graphite conducts electricity along the planes of carbon atoms, but does not conduct in a direction at right angle
In geometry and trigonometry, a right angle is an angle of exactly 90 degrees or radians corresponding to a quarter turn. If a ray is placed so that its endpoint is on a line and the adjacent angles are equal, then they are right angles. T ...
s to the plane.
Molecular orbitals
Standard ab initio quantum chemistry methods lead to delocalized orbitals that, in general, extend over an entire molecule and have the symmetry of the molecule. Localized orbitals may then be found as linear combinations of the delocalized orbitals, given by an appropriate unitary transformation
In mathematics, a unitary transformation is a transformation that preserves the inner product: the inner product of two vectors before the transformation is equal to their inner product after the transformation.
Formal definition
More precisely, ...
.
In the methane molecule, ab initio calculations show bonding character in four molecular orbitals, sharing the electrons uniformly among all five atoms. There are two orbital levels, a bonding molecular orbital formed from the 2s orbital on carbon and triply degenerate bonding molecular orbitals from each of the 2p orbitals on carbon. The localized sp3 orbitals corresponding to each individual bond in valence bond theory
In chemistry, valence bond (VB) theory is one of the two basic theories, along with molecular orbital (MO) theory, that were developed to use the methods of quantum mechanics to explain chemical bonding. It focuses on how the atomic orbitals of ...
can be obtained from a linear combination of the four molecular orbitals.
See also
*Aromatic ring current
An aromatic ring current is an effect observed in aromatic molecules such as benzene and naphthalene. If a magnetic field is directed perpendicular to the plane of the aromatic system, a ring current is induced in the delocalized π electrons ...
*Electride
An electride is an ionic compound in which an electron is the anion. Solutions of alkali metals in ammonia are electride salts. In the case of sodium, these blue solutions consist of a(NH3)6sup>+ and solvated electrons:
:Na + 6 NH3 → ...
*Solvated electron
A solvated electron is a free electron in (solvated in) a solution, and is the smallest possible anion. Solvated electrons occur widely. Often, discussions of solvated electrons focus on their solutions in ammonia, which are stable for days, but s ...
References
{{Authority control
Chemical bonding
Electron states