In an effort to find a p-benzyne (1,4-didehydrobenzene) derivative with a triplet ground state, we have investigated tetrasubstitution by -F, -NH(2), -CH(3), and -NO(2) groups. These were predicted to reduce the singlet-triplet gap, but none led to a triplet ground state because of unexpected destabilization of one of the radical orbitals. This effect is likely the result of rehybridization of the substituted C atom, which has been observed for substituted benzene and perturbs the side sigma and sigma* orbital energies of the phenyl ring. The role of substituent rotation on the energy difference between the two nominally singly occupied orbitals (S and A) was then investigated. The energy of the A radical orbital was found to be much more sensitive to perturbations within the sigma C[bond]C framework than the S MO. Consequently, we believe that rehybridization of the ring carbons destabilizes the A radical orbital and can lead to large singlet-triplet splittings. To test this hypothesis, calculations on a p-benzyne with 2,6 substitution by oxygen were performed. Interestingly, a triplet ground state was predicted. Yet, examination of the geometry and wave function showed that 2,6-quinone p-benzyne is a very twisted molecule with a C3-C4-C5 allene linkage and a C1 triplet carbene center.