RESONANCE 1.

INTRODUCTION: Resonance in chemistry is a theory used to represent and model certain

types of non-classical molecular structures resonance is the tendency of a system to oscillate at maximum amplitude at certain frequencies, known as the system's resonance frequencies (or resonant frequencies)

Resonance in chemistry is a tool used (predominately in organic chemistry) to represent certain types of molecular structures. 2. Resonance and its chemistry:
When damping is small, the resonance frequency is approximately equal to the natural frequency of the system, which is the frequency of free vibrations. Resonance is a key component of valence bond theory and arises when no single conventional model using only even number of electrons shared exclusively by two atoms can actually represent the observed molecule

Resonance is used to represent the stabilization of the molecule in

diagrams.

3 . Resonance as a diagrammatic tool

Scheme 1. Resonance structures of benzene

A single Lewis structure often cannot represent the true electronic structure of a molecule. While one can only show an integral number of covalent bonds between two and only two atoms using these diagrams, one often finds that the experimentally deduced or calculated (from Quantum mechanics) structure of the molecule does not match any of the possible Lewis structures but rather has properties in some sense intermediate to these. Resonance structures are then employed to approximate the true electronic structure. Take the

example of benzene (shown above, right). In a Lewis diagram, two carbons can be connected by one or two covalent bonds, but in the observed benzene molecule the carboncarbon bond lengths are 139 pm, longer than typical C=C double bonds (133 pm) yet shorter than typical C-C single bonds (154 pm). More importantly, they are all equivalent, a fact no Lewis structure can explain. Therefore one calls the two Lewis structures canonical, contributing or resonating structures and the real molecule is considered to be their average, called a resonance hybrid. Resonance structures of the same molecule are connected with a double-headed arrow. This form of resonance is simply a way of representing the structure graphically. It is only a notation and does not represent a real phenomenon. The individual resonance structures do not exist in reality: the molecule does not inter-convert between them. Instead, the molecule exists in a single unchanging state, intermediate between the resonance structures and only partially described by any one of them. This sharply distinguishes resonance from tautomerism. When it is said that a molecule is stabilized by resonance or that amides are less basic because the lone pair on nitrogen is involved in resonance with the carbonyl pi electron, no phenomenon is implied. What is meant is simply that the molecule behaves differently from what we expect by looking at its Lewis structure because the structure diagrammed does not represent the actual structure of the molecule. From this viewpoint, the terminology treating resonance as something that 'happens' is perhaps an unfortunate historical burden. It is also not correct to say that resonance occurs because electrons "flow", "circulate", or change their place within the molecules. Such a behavior would produce a magnetic field, an effect that is not observed in reality. However, a phenomenon of this sort may be induced by the application of an external magnetic field perpendicular to the plane of an aromatic ring: this causes the appearance of an opposing magnetic field, demonstrating that that the delocalised pi electrons are truly flowing. The applied magnetic field induces a current density ("ring current") of circulating electrons in the pi system; this current in turn induces a magnetic field. A common manifestation of this effect is the large chemical shift observed in the NMR spectrum of aromatic structures.

A vector analogy
An accurate analogy of resonance is given by the algebra of vectors. A vector r is written in component form as xi+yj+zk where x, y, and z are components and i, j, and k are the standard orthogonal Cartesian unit vectors. Just as the real vector r is neither i, nor j, nor k, but rather a combination of all three, a resonance hybrid is a conceptual combination of

resonance structures. x, y, and z have no independent existence; they are considered only as a decomposition of r into easier-to-handle components, as is the case with resonance structures. In fact this analogy is very close to the reality, as will be made clear in the following section.

True nature of resonance

Though resonance is often introduced in such a diagrammatic form in elementary chemistry, it actually has a deeper significance in the mathematical formalism of valence bond theory(VB). When a molecule cannot be represented by the standard tools of valence bond theory (promotion, hybridisation, orbital overlap, sigma and pi bond formation) because no single structure predicted by VB can account for all the properties of the molecule, one invokes the concept of resonance. Valence bond theory gives us a model for benzene where each carbon atom makes two sigma bonds with its neighbouring carbon atoms and one with a hydrogen atom. But since carbon is tetravalent, it has the ability to form one more bond. In VB it can form this extra bond with either of the neighbouring carbon atoms, giving rise to the familiar Kekul ring structure. But this cannot account for all carbon-carbon bond lengths being equal in benzene. A solution is to write the actual wavefunction of the molecule as a linear superposition of the two possible Kekul structures (or rather the wavefunctions representing these structures), creating a wavefunction that is neither of its components but rather a superposition of them, just as in the vector analogy above (which is formally equivalent to this situation). In benzene both Kekul structures have equal weight, but this need not be the case. In general, the superposition is written with undetermined constant coefficients, which are then variationally optimized to find the lowest possible energy for the given set of basis wavefunctions. This is taken to be the best approximation that can be made to the real structure, though a better one may be made with addition of more structures. In molecular orbital theory, the main alternative to VB, resonance often (but not always) translates to a delocalization of electrons in pi orbitals (which are a separate concept from pi bonds in VB). For example, in benzene, the MO model gives us 6 pi electrons completely delocalised over all 6 carbon atoms, thus contributing something like half-bonds. This MO interpretation has inspired the picture of the benzene ring as a hexagon with a circle inside. Often when describing benzene the VB picture and the MO picture are intermixed, talking both about localized sigma 'bonds' (strictly a concept from VB) and 'delocalized' pi electrons (strictly a concept from MO).

[edit]Resonance

energy

Resonance hybrids are always more stable than any of the canonical structures would be, if they existed[1]. The delocalization of the electrons lowers the orbital energies, imparting this stability. The resonance in benzene gives rise to the property of aromaticity. The gain in stability of the resonance hybrid over the most stable of the (non-existent) canonical structures is called the resonance energy. A canonical structure that is lower in energy makes a relatively greater contribution to the resonance hybrid, or the actual picture of the molecule. In fact, resonance energy, and consequently stability, increase with the number of canonical structures possible, especially when these (non-existent) structures are equal in energy. Resonance energy of a conjugated system can be 'measured' by heat of hydrogenation of the molecule. Consider the example of benzene. The energy required to hydrogenate an isolated pi-bond is around 28.6 kcal/mol (120 kJ/mol). Thus, according to the VB picture of benzene (having three pi-bonds), the complete hydrogenation of benzene should require 85.8 kcal/mol (360 kJ/mol). However, the experimental heat of hydrogenation of benzene is around 49.8 kcal/mol (210 kJ/mol). The difference of 36 kcal/mol (150 kJ/mol) can be looked upon as a measure of resonance energy. One must bear in mind again that resonance structures have no physical existence. So, even though the term 'resonance energy' is quite meaningless, it offers an insight into how different the VB picture of a molecule is from the actual molecule itself. The resonance energy can be used to calculate electronegativities on the Pauling scale.

Writing resonance structures

1. Position of nuclei must be the same in all structures, otherwise they would be

isomers with real existence. 2. 3. Total number of electrons and thus total charge must be constant. When separating charge (giving rise to ions), usually structures where

negative charges are on less electronegative elements have little contribution, but this may not be true if additional bonds are gained. 4. Resonance hybrids can not be made to have lower energy than the actual

molecules.

History
The concept of resonance was introduced by Linus Pauling in 1928. The term "resonance" came from the analogy between the quantum mechanical treatment of the H2 molecule and

a classical system consisting of two coupled 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. The alternative term mesomerism popular in German and French publications with the same meaning was introduced by Christopher 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 Arndt (also responsible for the Arndt-Eistert synthesis) who preferred the German phrase zwischenstufe or intermediate phase. Due to confusion with the physical meaning of the word resonance, as no elements actually appear to be resonating, it has been suggested that the term resonance be abandoned in favor of delocalization.[2] Resonance energy would become delocalization energy and a resonance structure becomes a contributing structure. The double headed arrows would be replaced by commas. [edit]Examples

Scheme 2. Examples of resonance ozone, benzene and the allyl cation

The ozone molecule is represented by two resonance structures in the top of scheme 2. In reality the two terminal oxygen atoms are equivalent and the hybrid structure is drawn on the right with a charge of -1/2 on both oxygen atoms and partial double bonds. The concept of benzene as a hybrid of two conventional structures (middle scheme 2) was a major breakthrough in chemistry made by Kekul, and the two forms of the ring which together represent the total resonance of the system are called Kekul structures. In the hybrid structure on the right the circle replaces three double bonds, and represents six electrons in a set of three molecular orbitals of pi symmetry, with a nodal plane in the plane of the molecule.

[edit]Reactive

intermediates

Often, reactive intermediates such as carbocations and free radicals have more delocalised 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-2butene. 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 asNMR in superacid solutions) shows that the intermediate carbocation must have a highly delocalised structure, different from its mostly classical (delocalisation exists but is small) parent molecule. This cation (an allylic cation) can be represented using resonance, as shown above. This observation of greater delocalisation 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. An well-studied example of delocalisation that does not involve pi electrons (hyperconjugation) can be observed in the non-classical ion norbornyl cation. Other examples are diborane andmethanium (CH5+). These are known as 3-center-2-electron bonds and are represented either by resonance structures involving rearrangement of sigma electrons or by a special notation, a Y that has the three nuclei at its three points.

Resonance
Main article: Resonance structure For some molecules and ions, it is difficult to determine which lone pairs should be moved to form double or triple bonds. This is sometimes the case when multiple atoms of the same type surround the central atom, and is especially common for polyatomic ions. When this situation occurs, the molecule's Lewis structure is said to be a resonance structure, and the molecule exists as a resonance hybrid. Each of the different possibilities is superimposed on the others, and the molecule is considered to have a Lewis structure equivalent to an average of these states. The nitrate ion (NO3-), for instance, must form a double bond between nitrogen and one of the oxygens to satisfy the octet rule for nitrogen. However, because the molecule is symmetrical, it does not matter which of the oxygens forms the double bond. In this case, there are three possible resonance structures. Expressing resonance when

drawing Lewis structures may be done either by drawing each of the possible resonance forms and placing double-headed arrows between them or by using dashed lines to represent the partial bonds. When comparing resonance structures for the same molecule, usually those with the fewest formal charges contribute more to the overall resonance hybrid. When formal charges are necessary, resonance structures that have negative charges on the more electronegative elements and positive charges on the less electronegative elements are favored.

Resonance hybridization
In Lewis resonance structures, the structure is written such that it appears the molecule may switch between multiple forms. However, the molecule itself exists as a hybrid of the forms. In the case of the nitrate ion, there are two single bonds and one double bond in each resonance form. When the nitrate ion is examined, however, each bond appears as though it has a bond order of 1.333that is, each has properties as if it were composed of one and one-third total bonds. The length and bond energy of each is somewhere between that of a single bond and a double bond. The resonance structure should not be interpreted to indicate that the molecule switches between forms, but that the molecule acts as the average of multiple forms.

What is a resonance in Quantum Mechanics? A resonance is a quantum state* which mean energy lies above the fragmentation threshold of a system and is associated with

a pronounced variation of the cross sections if the fragmentation energy lies in the neighbourhood of the energy of the resonance (energy-dependent definition) - The width of this neighbourhood is called the width of the resonance. a measurable delay of the fragmentation of the system when the system has a mean energy close to the resonance energy (time-dependent definition) - The lifetime (or time delay) of the resonance is proportional to the inverse of its width. Resonances are usually classified into shape and Feshbach resonances.

IMAGES

Resonance Theory (c. 1945)

There are several pages on the Avogadro Web Site that refer to the delocalisation of electrons within chemical structures. Where this has been observed, some additional stability has been associated with the structures concerned. What follows is a brief insight into Resonance Theory.

Whilst it is common to represent a chemical structure in a consistent and recognisable way, often the structural formula shown does not adequately represent the distribution of electrons within it. Rather, it is necessary to represent the molecule (or ion) by various alternative structures, with the true structure, and its distribution of electrons, lying somewhere between the extremes. Benzene provides a first example The benzene molecule is often represented as a hexagonal ring of alternate single and double carboncarbon bonds. But, given one such structure drawn on paper, the single and double bonds can be shown to have changed positions simply by re-distributing the pairs of electrons. These are the two Kekul structures of benzene.

Move the mouse across the structure to change between the Kekul forms of benzene.

The true structure of benzene lies somewhere in between the Kekul forms, and is referred to as a RESONANCE HYBRID of these.

It is essential to appreciate this idea; above all else, it is important to realise the resonance hybrid is not a mixture of the canonical forms, nor that the forms are rapidly alternating from one to another in a dynamic equilibrium.

The different structures contributing to the resonance hybrid are referred to as CANONICAL FORMS of the molecule. The more stable a canonical form, the more it contributes to the resonance hybrid. The resonance hybrid is more stable than any one of its canonical forms, and the difference in energy between the resonance hybrid and the most stable canonical form is known as the RESONANCE ENERGY orDELOCALISATION ENERGY. Generally, the greater the number of canonical forms of about the same energy, the greater the resonance energy. Modern physical analysis confirms the resonance hybrid nature of benzene. A simple and convenient way of representing the benzene ring is to place a circle inside the hexagonal ring.

Resonance Energy of Benzene Add a little liquid bromine to an alkene, such as cyclohexene, and an immediate reaction is observed. An electrophilic addition reaction occurs with the decolorisation of the bromine. Add liquid bromine to benzene and no such similar observation is made. If a reaction is taking place then it does so very slowly indeed. Now add some iron filings or iron(III) bromide and the formation of white fumes of hydrogen bromide gas is a sign of a reaction, in which electrophilic substitution is taking place. This is an illustration of the additional stability afforded to the benzene ring owing to the delocalisation of electrons. The resonance energy of benzene can be determined by comparing the enthalpies of hydrogenation of benzene and cyclohexene. If benzene did have the hypothetical 'cyclohexatriene' structure (the Kekul structure), then it would be expected to have an enthalpy of hydrogenation that is three times that of cyclohxene.

The enthalpy of hydrogenation of cyclohxene is -121 kJ mol-1, providing a theoretical value of -363 kJ mol1 for Kekul benzene with its three separate carbon-carbon double bonds.

In fact, the actual enthalpy of hydrogenation of benzene is only -209 kJ mol-1. Therefore, 154 kJ mol-1 of energy less than might have been expected is evolved. This is the energy that must have been expended in overcoming the additional stability conferred upon the benzene ring, owing the delocalisation of electrons. It is called the resonance energy or delocalisation energy. In general, substances in which electrons are fairly evenly distributed over the entire or part of the molecules tend to be more stable and less reactive than those in which electrons are localised. This is because the polarity of chemical bonds is kept to a minimum, making bond breaking more difficult. Here's another example Ethanoic acid, Phenol, and Ethanol can be considered as weak acids. Their relative strengths as acids are:

Ethanoic acid > Phenol > (Water) > Ethanol

This can be explained (in part) in terms of the stability of their respective conjugate bases; the more stable a base, the greater in the tendency for it to form. The relative base strengths are:

Ethoxide ion > Phenoxide ion > (Hydroxide ion) > Ethanoate ion
Both the Ethanoate ion, CH3COO-, and the Phenoxide ion, C6H5O-, allow for some delocalisation of electrons in their structures. There is no such delocalisation of electrons in the Ethoxide ion, CH3CH2O-. The diagrams below attempt to illustrate the delocalisation of electrons in the anions where this exists. The comparative stability of the Ethanoate ion is attributable to the delocalisation of electrons as represented by the two canonical forms.Move the mouse pointer over the canonical forms to represent them as a single resonance hybrid structure. This structure also illustrates the equivalence of both carbon-oxygen bonds and the equal distribution of negative charge between the oxygen atoms.

The Phenoxide ion is also stabilised by resonance. The lone pair of oxygen electrons are considered to interact with, and form part of, the delocalised electron system of the benzene ring. Move the mouse pointer over the canonical forms to represent them as a single resonance hybrid structure.

The ability of alcohols to liberate hydrogen in their reaction with alkali metals illustrates their acidic nature, but their acidic strengths are much weaker than even that of water. Ethanol, for example, is a weaker acid than Phenol which in turn is a weaker acid than Ethanoic acid. There is no delocalisation of electrons in the Ethoxide ion.

What is a shape resonance? In contrast with a Feshbach resonance, a shape resonance is a resonance which is not turned into a bound state if the coupling between some degrees of freedom and the degrees of freedom associated to the fragmentation (reaction coordinates) were set to zero. Of course in one-dimensional systems, resonances are shape resonances. In a system with more than one degree of freedom, this definition makes sense only if the separable model, which supposes the two groups of degrees of freedom uncoupled, is a meaningfull approximation. When the coupling becomes large, the situation is much less clear (see J. Chem. Phys. 116 (2002) 8318-8326, J. Chem. Phys. 104 (1996) 2222-2236, or J. Chem. Phys. 103 (1995) 45244537)
FESHBACH RESONANCE: In contrast with a shape resonance, a Feshbach resonance is a resonance of a system, with more than one degree of freedom, which would turn into a bound state if the coupling between some degrees of freedom and the degrees of freedom associated to the fragmentation (reaction coordinates) were set to zero. IMAGES:

"Resonance effect shown for various input frequencies and damping coefficients."
Theory
For a linear oscillator with a resonance frequency , the intensity of oscillations I when the system is driven with a driving frequency is given by:

The intensity is defined as the square of the amplitude of the oscillations. This is a Lorentzian function, and this response is found in many physical situations involving resonant systems. is a parameter dependent on the damping of the oscillator, and is known as the linewidth of the resonance. Heavily damped oscillators tend to have broad linewidths, and respond to a wider range of driving frequencies around the resonance frequency. The linewidth is inversely proportional to the Q factor, which is a measure of the sharpness of the resonance.