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The failure of certain LCAO molecular orbital calculations of the spectrum of porphine is attributed to the incorrect assumption of complete ``aromaticity.'' A division of the π-electron system into non-interacting parts is supported by the fact that the dynamical properties of the divided system, as calculated by the free-electron model, are in approximate agreement with experiment. A proof of the equivalency of the LCAO method (with overlap neglected) and an approximation to the free-electron method is indicated for certain dynamical systems.
William T. Simpson (Thu,) studied this question.
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