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.
Past exam of the chemistry A course of the University of Cambridge 2023 Paper 1 A5 a ii Solution 2026-10-20
Filling the three bonding molecular orbitals with two electrons each givesThree isolated ethene-like bonds, evaluated with the same Hückel method parameters, have . Thus the signed delocalization energy isEquivalently, 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.
Past exam of the chemistry A course of the University of Cambridge 2023 Paper 1 A5 b iv Solution 2026-10-20
The six electrons give the Hückel method energyThe 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 iswhose eigenvalues are . Since , the occupied bonding molecular orbital has energy . Two doubly occupied C=N bonds and one doubly occupied C=C bond consequently giveTherefore the signed delocalization energy isThe 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.