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These should try to delocalize over the whole molecule.
This allows the "pi" electrons to delocalize over large areas.
The ability to hop (to delocalize) reduces the kinetic energy.
What it all comes down to is that molecules form because electrons can then delocalize to a greater extent than they can in isolated atoms.
Resonance structures can be drawn to delocalize both negative and positive charges onto any terminus of a 1,3-dipole (see the scheme below).
Protonation helps to delocalize the otherwise trapped diiminoquinone-diaminobenzene state.
A spherical fullerene of n carbon atoms has n pi-bonding electrons, free to delocalize.
Of course, the actual details of when electrons can delocalize more and when less is dreadfully complicated, which is why theoretical chemists have jobs.
Buckminsterfullerene does not exhibit "superaromaticity": that is, the electrons in the hexagonal rings do not delocalize over the whole molecule.
One, an expected chemical reaction may not occur because the electrons delocalize to a more stable configuration, resulting in a reaction that happens at a different location.
The π orbitals of an alkene can stabilize a transition state by helping to delocalize the positive charge of the carbocation.
In non-conductors, aka insulators, the conduction band is higher than that of the valence band, so it takes infeasibly high energies to delocalize their valence electrons.
Unlike the related 5-membered heterocycles pyrrole, thiophene, and furan, the aromaticity of phospholes is diminished, reflecting the reluctance of phosphorus to delocalize its lone pair.
Protonophores are generally aromatic compounds that are both hydrophobic and capable of distributing the negative charge over a number of atoms by π-orbitals which delocalize a proton's charge in the molecule.
It is, however, debatable whether diaryl carbenes such as the fluorene carbene are true carbenes because the electrons can delocalize to such an extent that they become in fact biradicals.
They delocalise electron density from the non-bonding lone pair on carbon (the highest occupied molecular orbital).
For instance in the following alkyl benzenesulfonate the alkene is able to delocalise the carbocation.