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Intramolecular charge transfer in π-conjugated oligomers: a theoretical study on the effect of temperature and oxidation state

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Abstract

Intramolecular charge transfer (ICT) of gaseous π-conjugated oligo-phenyleneethynylenes (OPE) induced by a homogeneous applied electric field has been theoretically investigated using a combined approach integrating molecular dynamics (MD) simulations and Perturbed Matrix Method calculations. In line with recent investigations, our results indicate the peculiar role of conformational transitions on OPE electronic properties which reflects on a strong temperature effect on ICT. Electron transfer reactions inducing chemical alteration on OPE, also taken into account in this study, revealed extremely important for explaining non-linear ICT effects and probably plays a central role in the mechanisms underlying molecular transport junctions. Our study further points out the necessity of using MD-based approach for modelling molecular electronics, even when relatively rigid molecular systems are concerned.

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Authors and Affiliations

  1. Dipartimento di Chimica, Ingegneria Chimica e Materiali Universita’ di L’Aquila, Via Vetoio (Coppito), 67010, L’Aquila, Italia

    Massimiliano Aschi

  2. Dipartimento di Chimica, Universita’ di Roma ‘La Sapienza’, P.le A. Moro 5, 00185, Roma, Italia

    Maira D’Alessandro, Alfredo Di Nola & Marco D’Abramo

  3. Dipartimento di Ingegneria Elettronica, Universita’ di Roma‘La Sapienza’, Via Eudossiana 18, 00184, Roma, Italia

    Monica Pellegrino

  4. Barcelona Supercomputing Center, Torre Girona, c/ Jordi Girona, 31, 08034, Barcelona, Spain

    Marco D’Abramo

  5. Dipartimento di Scienze e Tecnologie Chimiche, Universita’ di Roma ‘Tor Vergata’, Via della Ricerca Scientifica 1, 00133, Roma, Italy

    Andrea Amadei

Authors
  1. Massimiliano Aschi
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  2. Maira D’Alessandro
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  3. Monica Pellegrino
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  4. Alfredo Di Nola
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  5. Marco D’Abramo
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  6. Andrea Amadei
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Correspondence to Massimiliano Aschi or Andrea Amadei.

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Aschi, M., D’Alessandro, M., Pellegrino, M. et al. Intramolecular charge transfer in π-conjugated oligomers: a theoretical study on the effect of temperature and oxidation state. Theor Chem Account 119, 469–476 (2008). https://doi.org/10.1007/s00214-007-0407-2

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  • DOI: https://doi.org/10.1007/s00214-007-0407-2

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