Abstract
A semiempirical algorithm for calculating exciton zones in polymers has been developed within the framework of the configuration interaction singles (CIS) method taking into account the interaction of all singly excited configurations. An illustrative method based on a transition density matrix is proposed to analyze electron‐excited states in periodic structures. Indices of intermonomer charge transfer and excitation localization on monomer fragments are introduced. A quantum‐chemical definition is given for the specific characteristics of an exciton transition, i.e., the excitation radius and the average exciton radius for the entire exciton zone. Concrete calculations for a series of polyphenylenevinylenes and polyaromatic systems indicate localization of excitations, in particular, of triplet ones, mainly on the central link and the nearest neighboring links of a polymer.
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Luzanov, A.V. Analysis of the Exciton States of Polyconjugated Systems by the Transition Density Matrix Method. Journal of Structural Chemistry 43, 711–720 (2002). https://doi.org/10.1023/A:1022884018770
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DOI: https://doi.org/10.1023/A:1022884018770