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Investigation of the torsional barrier of EDOT using molecular mechanics and DFT methods

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Abstract

When heterocyclic monomers are polymerized by electrochemical or chemical methods, they form fully conjugated polymers which have a wide range of applications due to their outstanding electronic properties. Among this class of compounds, thiophene derivatives are widely used due to their chemical stability and synthesis flexibility. With the goal to investigate the torsion barrier of polymer chains, a few units of 3,4-ethylenedioxythiophene (EDOT) were chosen and submitted to molecular mechanics (MM), density functional theory (DFT) and coupled cluster CCSD(T) calculations. This study helps to understand the performance and transferability of force fields used in molecular mechanics and molecular dynamics simulations often used to describe structure–property relationships of those systems. Determination of inter-ring torsion angle was performed in a comparative study using both force field, DFT and CCSD(T) methods. A good agreement was noticed between MM and QC results and highlights the importance of the description of the interactions involving the oxygen atoms present in the structure of EDOT. These observations are related to the α,α-coupling that occurs between the monomer units and yields a linear polymer. DFT HOMO and LUMO orbitals were also presented. Finally, UV–vis spectra of EDOT units were obtained using several levels of theory by means of time-dependent DFT calculations (TD-DFT).

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Acknowledgments

The authors are grateful for financial support of National Counsel of Technological and Scientific Development (CNPq) and Coordination of Improvement of Higher Education Personnel (Capes) Brazilian agencies. We also thank Prof. David Azevedo (IF-UnB) for his help with the COMPASS force field calculations.

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Authors and Affiliations

  1. Institute of Chemistry, University of Brasília, P.O. Box 04478, 70904-970, Brasília, Brazil

    Jussara A. Durães, Maria J. A. Sales & João B. L. Martins

  2. Institute of Physics, University of Brasília, P.O. Box 04455, 70919-970, Brasília, Brazil

    Demétrio A. da Silva Filho

  3. Department of Electric Engineering, University of Brasília, Brasília, Brazil

    Artemis M. Ceschin

Authors
  1. Jussara A. Durães
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  2. Demétrio A. da Silva Filho
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  3. Artemis M. Ceschin
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  4. Maria J. A. Sales
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  5. João B. L. Martins
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Correspondence to João B. L. Martins.

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This paper belongs to Topical Collection Brazilian Symposium of Theoretical Chemistry (SBQT2013)

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Durães, J.A., da Silva Filho, D.A., Ceschin, A.M. et al. Investigation of the torsional barrier of EDOT using molecular mechanics and DFT methods. J Mol Model 20, 2405 (2014). https://doi.org/10.1007/s00894-014-2405-3

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  • DOI: https://doi.org/10.1007/s00894-014-2405-3

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