RESONANCE The phenomenon of resonance was put forward by Heisenberg to explain the properties of certain molecules .

It is often observed that a single Lewis structure is inadequate for representation of a molecule in conformity with its experimentally determined parameters. For example ozone O3 , molecule can be equally well represented by the structures I and II shown below :

In both structures there is OO single bond and O=O double bond. The normal OO and O=O bond length are 148 pm and 121 pm respectively. Experimentally determined oxygenoxygen bond lengths in O3 molecule are same (128 pm ). Thus oxygen-oxygen bonds in O3 molecule are intermediate between a double bond and a single bond. This cannot be represented by either of the two Lewis structures shown above. According to the concept of resonance , whenever a single Lewis structure cannot describe a molecule accurately, a number of structures with similar energy , positions of nuclei, bonding and non-bonding pairs of electrons are taken as cannonical structures of the resonance hybrid which describes the molecule accurately . Thus, for O3, the two structures shown above constitute the cannonical structures and their hybrid represents the structure of O 3 more accurately. Resonance is represented by a double headed arrow .

Some other examples of resonance structures have been provided by the carbonate ion and the carbon dioxide molecule. Resonance in of CO32 According to the experimental findings , all carbon to oxygen bonds in CO 32 are equivalent. Therefore the carbonate ion is best described as a resonance hybrid of the cannonical forms I, II and III as shown below :

Resonance in CO2molecule The experimentally determined carbon to oxygen bond length in CO 2 is 115 pm. The lengths of a normal carbon to oxygen double bond (C=O) and carbon to oxygen triple bond (CO) are 121 pm and 110 pm respectively. The carbon-oxygen bond lengths in CO2 (115 pm) lie between the values for C=O and CO. a single Lewis structure cannot depict this position and it becomes necessary to write more than one Lewis structures and to consider that the structure of CO2 is best described as a resonance hybrid of the cannonical forms, I, II and III .

Characteristics of Resonance Resonance occurs because of the overlap of orbitals. Double bonds are made up of pi bonds, formed from the overlap of 2p orbitals. The electrons in these pi orbitals will be spread over more than two atoms, and hence are delocalized. Both paired and unshared electrons may be delocalized, but all the electrons must be conjugated in a pi system. Molecules or species with resonance structures are generally considered to be more stable than those without them. 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 is called the resonance energy. All resonance structures for the same molecule must have the same sigma framework (sigma bonds form from the "head on" overlap of hybridized orbitals). Furthermore, they must be correct Lewis structures with the same number of electrons (and consequent charge) as well as the same number of unpaired electrons. Resonance averages the bond characterisics as a whole. Thus the energy of the O3 resonance hybrid is lower than either of the two cannonical forms I and II . The individual structures of similar energy contribute equally to the resonance hybrid. Cannonical structures with somewhat higher energies may also contribute to the resultant hybrid, but the higher the energy of a particular structure, the lesser is its contribution. For example, in the example of benzene molecule (C6H6) the cannonical forms are :

The two equivalent Kekule forms and three equivalent Dewar forms (The energy of the Kekule forms is lower than the energy of the three Dewar forms) The contribution from the three equivalent Dewar high energy cannonical forms to the resonance hybrid representing benzene is lesser as compared to the contribution from the two equivalent lower energy Keule forms. The hybrid structure is defined as the superposition of the resonance structures.

Conditions for writing resonance structures: The following are essential conditions for writing resonance structures. 1. The contributing structures should have same atomic positions. 2. The contributing structures should have same number of paired and unpaired electrons.

3. The contributing structures should have nearly same energy content. 4. The structures should be so written that negative charge (if appearing) should reside on electronegative atom and positive charge on an electropositive atom. 5. In contributing structures, the like charges should not reside on adjacent atoms.
It should be noted that: The cannonical forms have no real existence. The molecule does not exist for a certain fraction of time in one cannonical form and other fractions of time in other cannonical forms. There is no such equilibrium between the cannonical forms. The molecules as such has a single structure which is the resonance hybrid of the cannonical forms and which cannot as such be depicted by a single Lewis structure.