In chemistry, resonance or mesomerism[1] is a way of describing delocalized electrons within

certain molecules or polyatomic ions where the bonding cannot be expressed by one single
Lewis structure. A molecule or ion with such delocalized electrons is represented by several
contributing structures[2] (also called resonance structures or canonical structures).

Each contributing structure can be represented by a Lewis structure, with only an integer number
of covalent bonds between each pair of atoms within the structure.[3] Several Lewis structures are
used collectively to describe the actual molecular structure, which is an approximate
intermediate between the canonical forms called a resonance hybrid.[4] Contributing structures
differ only in the position of electrons, not in the position of nuclei.

Electron delocalization lowers the potential energy of the substance and thus makes it more
stable than any of the contributing structures. The difference between the potential energy of the
actual structure and that of the contributing structure with the lowest potential energy is called
the resonance energy[5] or delocalization energy.

Resonance is distinguished from isomerization. An isomer is a molecule with the same chemical
formula but with different arrangements of atoms in space. Resonance contributors of a
molecule, on the contrary, can only differ by the arrangements of electrons. Therefore, the
resonance hybrid cannot be represented by a combination of isomers[6]

They can be represented by several correct Lewis formulas, called "contributing

structures", "resonance structures" or "canonical forms". The real structure is an
intermediate of these structures represented by a resonance hybrid.
The contributing structures are not isomers. They differ only in the position of electrons,
not in the position of nuclei.
Each Lewis formula must have the same number of valence electrons (and thus the same
total charge), and the same number of unpaired electrons, if any.[11]
Bonds that have different bond orders in different contributing structures do not have
typical bond lengths. Measurements reveal intermediate bond lengths.
The real structure has a lower total potential energy than each of the contributing
structures would have. This means that it is more stable than each separate contributing
structure would be.

The ozone molecule is represented by two resonance structures. In reality the two terminal
oxygen atoms are equivalent and the hybrid structure is drawn on the right with a charge of 12
on both oxygen atoms and partial double bonds with a full and dashed line and bond order
1 12.[15][16]

For hypervalent molecules such as xenon difluoride, the rationalization described above can be
applied to generate resonance structures to explain the bonding in such molecules. This has been
shown by quantum chemical calculations to be the correct description instead of the common
expanded octet model.[citation needed]

Aromatic molecules
Main article: Aromaticity

In benzene the two cyclohexatriene Kekul structures, first proposed by Kekul, are taken
together as contributing structures to represent the total structure. In the hybrid structure on the
right, the dashed hexagon replaces three double bonds, and represents six electrons in a set of
three molecular orbitals of symmetry, with a nodal plane in the plane of the molecule.

In furan a lone pair of the oxygen atom interacts with the orbitals of the carbon atoms. The
curved arrows depict the permutation of delocalized electrons, which results in different
contributors.

Electron-deficient molecules
Main article: Electron deficiency

The diborane molecule is described by resonance structures, each with electron-deficiency on

different atoms. This reduces the electron-deficiency on each atom and stabilizes the molecule.
Below are the resonance structures of an individual 3c-2e bond in diborane.

The allyl cation has two contributing structures with a positive charge on the terminal carbon
atoms. In the hybrid structure their charge is +12. The full positive charge can also be depicted as
delocalized among three carbon atoms.
Reactive intermediates
Main article: Reactive intermediate

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Often, reactive intermediates such as carbocations and free radicals have more delocalized
structure than their parent reactants, giving rise to unexpected products. The classical example is
allylic rearrangement. When 1 mole of HCl adds to 1 mole of 1,3-butadiene, in addition to the
ordinarily expected product 3-chloro-1-butene, we also find 1-chloro-2-butene. Isotope labelling
experiments have shown that what happens here is that the additional double bond shifts from
1,2 position to 2,3 position in some of the product. This and other evidence (such as NMR in
superacid solutions) shows that the intermediate carbocation must have a highly delocalized
structure, different from its mostly classical (delocalization exists but is small) parent molecule.
This cation (an allylic cation) can be represented using resonance, as shown above.

This observation of greater delocalization in less stable molecules is quite general. The excited
states of conjugated dienes are stabilised more by conjugation than their ground states, causing
them to become organic dyes.

A well-studied example of delocalization that does not involve electrons (hyperconjugation)

can be observed in the non-classical 2-Norbornyl cation. Other examples are diborane (see
above) and methanium (CH+
5). These can be viewed as containing three-center two-electron bonds and are represented either
by contributing structures involving rearrangement of electrons or by a special notation, a Y
that has the three nuclei at its three points.

Delocalized electrons are important for several reasons; a major one is that an expected chemical
reaction may not occur because the electrons delocalize to a more stable configuration, resulting
in a reaction that happens at a different location. An example is the FriedelCrafts alkylation of
benzene with 1-chloro-2-methylpropane; the carbocation rearranges to a tert-butyl group
stabilized by hyperconjugation, a particular form of delocalization. Delocalization leads to
lengthening of wavelength of electron therefore decreases the energy.
Bond lengths

Resonance structures of benzene

Comparing the two contributing structures of benzene, all single and double bonds are
interchanged. Bond lengths can be measured, for example using X-ray diffraction. The average
length of a CC single bond is 154 pm; that of a C=C double bond is 133 pm. In localized
cyclohexatriene, the carboncarbon bonds should be alternating 154 and 133 pm. Instead, all
carboncarbon bonds in benzene are found to be about 139 pm, a bond length intermediate
between single and double bond. This mixed single and double bond (or triple bond) character is
typical for all molecules in which bonds have a different bond order in different contributing
structures. Bond lengths can be compared using bond orders. For example, in cyclohexane the
bond order is 1 while that in benzene is 1 + (3 6) = 1 12. Consequently, benzene has more
double bond character and hence has a shorter bond length than cyclohexane.

Resonance energy
Every structure is associated with a certain quantity of energy, which determines the stability of
the molecule or ion (the lower energy, the greater stability). A resonance hybrid has a structure
that is intermediate between the contributing structures; the total quantity of potential energy,
however, is lower than the intermediate and the molecule is said to be "stabilized by resonance"
or "resonance-stabilized". Hybrids are therefore always more stable than any of the contributing
structures would be.[17] The difference between the potential energy of the actual structure (the
resonance hybrid) and that of the contributing structure with the lowest potential energy is called
the "resonance energy".[5]

Resonance energy of benzene

Resonance (or delocalization) energy is the amount of energy needed to convert the true
delocalized structure into that of the most stable contributing structure. The empirical resonance
energy can be estimated by comparing the enthalpy change of hydrogenation of the real
substance with that estimated for the contributing structure.
The complete hydrogenation of benzene to cyclohexane via 1,3-cyclohexadiene and cyclohexene
is exothermic; 1 mole of benzene delivers 208.4 kJ (49.8 kcal).

Hydrogenation of one mole of double bonds delivers 119.7 kJ (28.6 kcal), as can be deduced
from the last step, the hydrogenation of cyclohexene. In benzene, however, 23.4 kJ (5.6 kcal) are
needed to hydrogenate one mole of double bonds. The difference, being 143.1 kJ (34.2 kcal), is
the empirical resonance energy of benzene. Because 1,3-cyclohexadiene also has a small
delocalization energy (7.6 kJ or 1.8 kcal/mol) the net resonance energy, relative to the localized
cyclohexatriene, is a bit higher: 151 kJ or 36 kcal/mol. [18]

This measured resonance energy is also the difference between the hydrogenation energy of
three 'non-resonance' double bonds and the measured hydrogenation energy:

(3 119.7) 208.4 = 150.7 kJ/mol (36 kcal).[19]

Resonan ce in valence bond (VB) theory

VB mixing diagram of benzene.[20] The A1g and B2u labels define the symmetries of the two states, as
defined by the character table for the D6h symmetry group.
Resonance has a deeper significance in the mathematical formalism of valence bond theory
(VB). Quantum mechanics requires that the wavefunction of a molecule obeys its observed
symmetry. If a single contributing structure does not achieve this, resonance is invoked.

For example, in benzene, valence bond theory begins with the two Kekul structures and
constructs the actual wave function of the molecule as a linear superposition of the wave
functions representing the two structures. As both Kekul structures have equal energy, they are
equal contributors to the overall structure the superposition is an equally weighted average, or a
1:1 linear combination of the two but this need not be the case. The symmetric combination
gives the ground state while the antisymmetric combination gives the first excited state as
shown.

In general, the superposition is written with undetermined coefficients, which are then
variationally optimized to find the lowest possible energy for the given set of basis wave
functions. When more contributing structures are included, the molecular wave function
becomes more accurate and more excited states can be derived from different combinations of
the contributing structures.

Comparison with molecular orbital (MO) theory

In molecular orbital theory, the main alternative to valence bond theory, the equivalent of the
symmetry-adapted linear combination role of resonance is the linear combination of atomic
orbitals. In MO theory, the molecular orbitals (MOs) are approximated as sums of all the atomic
orbitals (AOs) on all the atoms; there are as many MOs as AOs. Each AOi has a weighting
coefficient ci that indicates the AO's contribution to a particular MO. For example, in benzene,
the MO model gives us 6 MOs which are combinations of the 2pz AOs on each of the 6 C
atoms. Thus, each MO is delocalized over the whole benzene molecule and any electron
occupying an MO will be delocalized over the whole molecule. This MO interpretation has
inspired the picture of the benzene ring as a hexagon with a circle inside. When describing
benzene, the VB concept of localized sigma 'bonds' and the MO concept of 'delocalized'
electrons are frequently combined in elementary chemistry courses.

The resonance structures in the VB model are particularly useful in predicting the effect of
substituents on systems such as benzene. They lead to the models of resonance structures for
an electron-withdrawing group and electron-releasing group on benzene. The utility of MO
theory is that a quantitative indication of the charge from the system on an atom can be
obtained from the squares of the weighting coefficient ci on atom Ci. Charge qi c2
i. The reason for squaring the coefficient is that if an electron is described by an AO, then the
square of the AO gives the electron density. The AOs are adjusted (normalized) so that AO2 = 1,
and qi (ciAOi)2 c2
i. In benzene, qi = 1 on each C atom. With an electron-withdrawing group qi < 1 on the ortho and
para C atoms and qi > 1 for an electron-releasing groups