Abstract
It is shown that the particular bond alternation pattern of short chain polydiacetylene intermediates gives rise to the occurrence of two nonbonding and nearly degenerate π molecular orbitals (MOs) which are localized at the chain ends of the longer oligomers. These orbitals evolve with increasing chain length from the highest bonding and the lowest antibonding π MOs leading to a loss of the closed shell structure of the π system, which is characterized by an increasing admixture of a doubly excited configuration to the ground configuration. We present a Hartree-Fock scheme which optimizes the coefficients of this configurational mixing and the MO coefficients simultaneously. The configuration interaction (CI) calculation is reformulated in terms of a simple two-site Hubbard model in a localized basis.
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