Delocalization energy 2026-10-20
The change in energy on allowing a specified localized orbital reference to delocalize across a conjugated system. In a Hückel method calculation, the reference must use the same one-centre parameters and bond types as the delocalized molecule. With the signed convention , stabilization is negative; its positive magnitude is often also called the delocalization energy, so the sign convention must be stated.
Filling the three bonding molecular orbitals with two electrons each gives
Three isolated ethene-like bonds, evaluated with the same Hückel method parameters, have . Thus the signed delocalization energy is
Equivalently, the positive stabilization is .
Benzene has a planar cyclic conjugated system with six electrons, satisfying the count with . All three bonding molecular orbitals are filled and the antibonding levels are empty, giving the closed-shell stabilization associated with aromaticity. The conclusion uses the continuous cyclic overlap as well as the electron count.
The six electrons give the Hückel method energy
The appropriate localized reference contains two C=N bonds and one C=C bond. Three C=C bonds would incorrectly replace the nitrogen one-centre parameters. For one isolated C=N pair, the dimensionless matrix is
whose eigenvalues are . Since , the occupied bonding molecular orbital has energy . Two doubly occupied C=N bonds and one doubly occupied C=C bond consequently give
Therefore the signed delocalization energy is
The positive stabilization is , smaller than the benzene value in the stated model but still stabilizing.
Pyrazine is aromatic: its planar cyclic conjugated system contains six electrons and has a filled set of three bonding molecular orbitals. Each ring nitrogen contributes one electron; its in-plane lone pair is outside this system. The heteroatoms change orbital energies and coefficients without interrupting cyclic conjugation or the count. Aromaticity does not require the stabilization to equal benzene's.