Resonance (chemistry)
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 into a resonance hybrid in valence bond theory. It has particular value for analyzing delocalized electrons where the bonding cannot be expressed by one single Lewis structure. The resonance hybrid is the accurate structure for a molecule or ion; it is an average of the theoretical contributing structures.
Overview
Under the framework of valence bond theory, resonance is an extension of the idea that the bonding in a chemical species can be described by a Lewis structure. For many chemical species, a single Lewis structure, consisting of atoms obeying the octet rule, possibly bearing formal charges, and connected by bonds of positive integer order, is sufficient for describing the chemical bonding and rationalizing experimentally determined molecular properties like bond lengths, angles, and dipole moment. However, in some cases, more than one Lewis structure could be drawn, and experimental properties are inconsistent with any one structure. In order to address this type of situation, several contributing structures are considered together as an average, and the molecule is said to be represented by a resonance hybrid in which several Lewis structures are used collectively to describe its true structure. For instance, in NO2–, nitrite anion, the two N–O bond lengths are equal, even though no single Lewis structure has two N–O bonds with the same formal bond order. However, its measured structure is consistent with a description as a resonance hybrid of the two major contributing structures shown above: it has two equal N–O bonds of 125 pm, intermediate in length between a typical N–O single bond and N–O double bond. According to the contributing structures, each N–O bond is an average of a formal single and formal double bond, leading to a true bond order of 1.5. By virtue of this averaging, the Lewis description of the bonding in NO2– is reconciled with the experimental fact that the anion has equivalent N–O bonds.The resonance hybrid represents the actual molecule as the "average" of the contributing structures, with bond lengths and partial charges taking on intermediate values compared to those expected for the individual Lewis structures of the contributors, were they to exist as "real" chemical entities. The contributing structures differ only in the formal apportionment of electrons to the atoms, and not in the actual physically and chemically significant electron or spin density. While contributing structures may differ in formal bond orders and in formal charge assignments, all contributing structures must have the same number of valence electrons and the same spin multiplicity.
Because electron delocalization lowers the potential energy of a system, any species represented by a resonance hybrid is more stable than any of the contributing structures. Electron delocalization stabilizes a molecule because the electrons are more evenly spread out over the molecule, decreasing electron-electron repulsion. The difference in potential energy between the actual species and the energy of the contributing structure with the lowest potential energy is called the resonance energy or delocalization energy. The magnitude of the resonance energy depends on assumptions made about the hypothetical "non-stabilized" species and the computational methods used and does not represent a measurable physical quantity, although comparisons of resonance energies computed under similar assumptions and conditions may be chemically meaningful.
Molecules with an extended π system such as linear polyenes and polyaromatic compounds are well described by resonance hybrids as well as by delocalized orbitals in molecular orbital theory.
Resonance vs isomerism
Resonance is to be distinguished from isomerism. Isomers are molecules with the same chemical formula but are distinct chemical species with different arrangements of atomic nuclei in space. Resonance contributors of a molecule, on the other hand, can only differ in the way electrons are formally assigned to atoms in the Lewis structure depictions of the molecule. Specifically, when a molecular structure is said to be represented by a resonance hybrid, it does not mean that electrons of the molecule are "resonating" or shifting back and forth between several sets of positions, each one represented by a Lewis structure. Rather, it means that the set of contributing structures represents an intermediate structure, with a single, well-defined geometry and distribution of electrons. It is incorrect to regard resonance hybrids as rapidly interconverting isomers, even though the term "resonance" might evoke such an image. Symbolically, the double headed arrowA non-chemical analogy is illustrative: one can describe the characteristics of a real animal, the narwhal, in terms of the characteristics of two mythical creatures: the unicorn, a creature with a single horn on its head, and the leviathan, a large, whale-like creature. The narwhal is not a creature that goes back and forth between being a unicorn and being a leviathan, nor do the unicorn and leviathan have any physical existence outside the collective human imagination. Nevertheless, describing the narwhal in terms of these imaginary creatures provides a reasonably good description of its physical characteristics.
Due to confusion with the physical meaning of the word resonance, as no entities actually physically "resonate", it has been suggested that the term resonance be abandoned in favor of delocalization and resonance energy abandoned in favor of delocalization energy. A resonance structure becomes a contributing structure and the resonance hybrid becomes the hybrid structure. The double headed arrows would be replaced by commas to illustrate a set of structures, as arrows of any type may suggest that a chemical change is taking place.
Representation in diagrams
In diagrams, contributing structures are typically separated by double-headed arrows. The arrow should not be confused with the right and left pointing equilibrium arrow. All structures together may be enclosed in large square brackets, to indicate they picture one single molecule or ion, not different species in a chemical equilibrium.
Alternatively to the use of contributing structures in diagrams, a hybrid structure can be used. In a hybrid structure, pi bonds that are involved in resonance are usually pictured as curves or dashed lines, indicating that these are partial rather than normal complete pi bonds. In benzene and other aromatic rings, the delocalized pi-electrons are sometimes pictured as a solid circle.
History
The concept first appeared in 1899 in Johannes Thiele's "Partial Valence Hypothesis" to explain the unusual stability of benzene which would not be expected from August Kekulé's structure proposed in 1865 with alternating single and double bonds. Benzene undergoes substitution reactions, rather than addition reactions as typical for alkenes. He proposed that the carbon-carbon bond in benzene is intermediate of a single and double bond.The resonance proposal also helped explain the number of isomers of benzene derivatives. For example, Kekulé's structure would predict four dibromobenzene isomers, including two ortho isomers with the brominated carbon atoms joined by either a single or a double bond. In reality there are only three dibromobenzene isomers and only one is ortho, in agreement with the idea that there is only one type of carbon-carbon bond, intermediate between a single and a double bond.
The mechanism of resonance was introduced into quantum mechanics by Werner Heisenberg in 1926 in a discussion of the quantum states of the helium atom. He compared the structure of the helium atom with the classical system of resonating coupled harmonic oscillators. In the classical system, the coupling produces two modes, one of which is lower in frequency than either of the uncoupled vibrations; quantum mechanically, this lower frequency is interpreted as a lower energy. Linus Pauling used this mechanism to explain the partial valence of molecules in 1928, and developed it further in a series of papers in 1931-1933. The alternative term mesomerism popular in German and French publications with the same meaning was introduced by C. K. Ingold in 1938, but did not catch on in the English literature. The current concept of mesomeric effect has taken on a related but different meaning. The double headed arrow was introduced by the German chemist Fritz Arndt who preferred the German phrase zwischenstufe or intermediate stage.
Resonance theory dominated over competing Hückel method for two decades thanks to being relatively easier to understand for chemists without fundamental physics background, even if they couldn't grasp the concept of quantum superposition and confused it with tautomerism. Pauling and Wheland themselves characterized Erich Hückel's approach as "cumbersome" at the time, and his lack of communication skills contributed: when Robert Robinson sent him a friendly request, he responded arrogantly that he is not interested in organic chemistry.
In the Soviet Union, resonance theory – especially as developed by Pauling – was attacked in the early 1950s as being contrary to the Marxist principles of dialectical materialism, and in June 1951 the Soviet Academy of Sciences under the leadership of Alexander Nesmeyanov convened a conference on the chemical structure of organic compounds, attended by 400 physicists, chemists, and philosophers, where "the pseudo-scientific essence of the theory of resonance was exposed and unmasked".