Pathways for Photoinduced Charge Separation in DNA Hairpins

D. Beljonne, G. Pourtois, M. A. Ratner, J. L. Brédas*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

48 Scopus citations


By means of correlated quantum-chemical calculations, we explore the chain-length dependence of the electronic coupling for photoinduced charge separation in DNA hairpins associated to conjugated linkers. Pathways for charge transfer from the linker chromophore to a guanine site located at a well-defined distance along the DNA strand are identified. Importantly, these involve not only the frontier molecular orbitals of the interacting donor, bridge, and acceptor units, but also deeper lying orbitals possessing both the appropriate energy and the symmetry to overlap significantly. The relative efficiency of these channels is found to be sensitive to the chemical structure of the linker, leading to falloff parameters for the charge-transfer rates ranging from ∼0.4 to ∼1.2 Å-1.

Original languageEnglish (US)
Pages (from-to)14510-14517
Number of pages8
JournalJournal of the American Chemical Society
Issue number47
StatePublished - Nov 26 2003
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry


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