Resonance in Quantum Mechanics
Resonance 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 π 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 Kekulé 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 Kekulé structures (or rather the wavefunctions representing these structures), creating a wavefunction that is neither of its components but rather a superposition of them.
In benzene both Kekulé structures have equal energy and 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. 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 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.
Read more about this topic: Resonance (chemistry)
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