Reviewing Extrapolation Procedures of the Electronic Properties on the p-Conjugated Polymer Limit
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In this article, the extrapolation procedures of π−π* electronic transition energy on π-conjugated oligomers are reexamined. Different models, including the simplest coupled oscillator, the free electron, the Hückel approach, the molecular exciton model, and some specific fitting-functions, are compared using the transition energies derived from theoretical calculations on three thiophene-based oligomer series. Specifically, oligomers of up to 30 repeating units have been considered to include the saturation effects as a function of chain length. The coupled oscillator model of W. Kuhn and the fitting-function of Hirayama are the models that present the better suit on the transition energy interpolation as a function of chain length. Using only the first four oligomers of the series (n = 2 up to 8) yields an estimation of the transition energy on the polymer limit with an average error of ∼1.5%. The vertical and adiabatic ionization potential present a better fit with the Hückel model approach. Finally, implications of the environmental polarity on the electronic properties, molecular geometry, charge distribution, and aromaticity are shortly discussed.
CitacióTorras, J.; Casanovas, J.; Alemán, C. Reviewing Extrapolation Procedures of the Electronic Properties on the p-Conjugated Polymer Limit. "Journal of physical chemistry A", 19 Juny 2012, vol. 116, núm. 28, p. 7571-7583.
Versió de l'editorhttp://pubs.acs.org/doi/abs/10.1021/jp303584b
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