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Molecular dipole effects on tuning electron transfer in a porphine–quinone complex: a DFT and TDDFT study

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Abstract

The effect of a strong electric field generated by molecular dipoles on the ground state electronic structure and the Q and B states as well as the lowest charge transfer (CT) excited state of porphine–2,5-dimethyl-1,4-benzoquinone (PQ) complex has been investigated theoretically. Density functional theory DFT and time-dependent DFT (TDDFT) with the BH&HLYP hybrid functional have been applied in these calculations. The molecular dipole effect was generated by imposing one or two helical homopeptides consisting of eight α-aminoisobutyric acid residues (Aib8) close to the PQ complex. The molecular dipoles in a close proximity to the PQ complex expose it to an electric field of the order of magnitude of 109 V/m. The presence of the ambient molecular dipoles affects mainly the energy of the lowest CT state and barely the energies of the Q and B states. The molecular dipoles affect the energies of the excited states in a similar way as an external electrostatic field. Hence, the electric field induced by the molecular dipoles of the helical peptides could be used analogously to the external electrostatic field to control electron transfer (ET) in the PQ complex.

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Acknowledgments

Prof. H. Lemmetyinen, the head of the Laboratory of Chemistry at Tampere University of Technology, is acknowledged for offering the facilities for this research. Computing resources provided by the CSC – IT Center for Science Ltd, administrated by the Finnish Ministry of Education, are acknowledged. Financing of this research by the Academy of Finland is greatly appreciated.

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Authors and Affiliations

  1. Department of Physics, Tampere University of Technology, P.O. Box 692, 33101, Tampere, Finland

    Oana Cramariuc

  2. Department of Chemistry and Bioengineering, Tampere University of Technology, P.O. Box 541, 33101, Tampere, Finland

    Pekka J. Aittala & Terttu I. Hukka

  3. IT Center for Science and Technology, Av. Radu Beller 25, Bucharest, Romania

    Oana Cramariuc

Authors
  1. Oana Cramariuc
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  2. Pekka J. Aittala
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  3. Terttu I. Hukka
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Correspondence to Terttu I. Hukka.

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Cramariuc, O., Aittala, P.J. & Hukka, T.I. Molecular dipole effects on tuning electron transfer in a porphine–quinone complex: a DFT and TDDFT study. J Mol Model 19, 697–704 (2013). https://doi.org/10.1007/s00894-012-1595-9

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  • DOI: https://doi.org/10.1007/s00894-012-1595-9

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