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Excess charge delocalization in organic and biological molecules: some theoretical notions

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Abstract

Theoretical and computational investigations of the excess charge distribution (ECD) in molecular complexes have attracted considerable attention as ECD is closely related to electronic properties of organic semiconductors, such as the efficiency of photoinduced charge separation in organic solar cells and charge transport in DNA and proteins. In this paper, we analyze the ECD in several representative models on the basis of ab initio and DFT calculations. We consider how changes in the reorganization energy, electronic coupling and charge transfer energy affect the ECD in the systems. In particular, we compare ECD in π stacks of polycyclic aromatic hydrocarbons and DNA nucleobases. While the π interaction between subunits in the systems is similar in both cases, ECD is quite different: the excess charge is found to be completely delocalized over the hydrocarbon stacks but strongly confined to a single nucleobase in DNA stacks. We also discuss the effects of conformational fluctuations on ECD in the stacks. Finally, ECD in amino acids and its dependence on the conformational changes are briefly considered.

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Acknowledgments

This work has been financially supported by the Spanish Ministerio de Educación y Ciencia Projects no. CTQ2005-04563, CTQ2005-08797-C02 and CTQ2008-03077/BQU. J.P. thanks the MEC for the Ramón y Cajal contract.

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Authors and Affiliations

  1. Institut de Química Computational and Departament de Química, Universitat de Girona, 17071, Girona, Spain

    Lluís Blancafort, Miquel Duran, Jordi Poater, Pedro Salvador, Sílvia Simon, Miquel Solà & Alexander A. Voityuk

  2. Institució Catalana de Recerca i Estudis Avançats, 08010, Barcelona, Spain

    Alexander A. Voityuk

Authors
  1. Lluís Blancafort
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  2. Miquel Duran
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  3. Jordi Poater
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  4. Pedro Salvador
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  5. Sílvia Simon
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  6. Miquel Solà
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  7. Alexander A. Voityuk
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Correspondence to Alexander A. Voityuk.

Additional information

Dedicated to Professor Santiago Olivella on the occasion of his 65th birthday and published as part of the Olivella Festschrift Issue.

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Blancafort, L., Duran, M., Poater, J. et al. Excess charge delocalization in organic and biological molecules: some theoretical notions. Theor Chem Acc 123, 29–40 (2009). https://doi.org/10.1007/s00214-009-0538-8

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  • DOI: https://doi.org/10.1007/s00214-009-0538-8

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