Absolute rates of hole transfer in DNA

Kittusamy Senthilkumar, Ferdinand C. Grozema, Célia Fonseca Guerra, F. Matthias Bickelhaupt, Frederick D. Lewis, Yuri A. Berlin, Mark A. Ratner, Laurens D A Siebbeles

Research output: Contribution to journalArticlepeer-review

308 Scopus citations


Absolute rates of hole transfer between guanine nucleobases separated by one or two A:T base pairs in stilbenedicarboxamide-linked DNA hairpins were obtained by improved kinetic analysis of experimental data. The charge-transfer rates in four different DNA sequences were calculated using a density-functional-based tight-binding model and a semiclassical superexchange model. Site energies and charge-transfer integrals were calculated directly as the diagonal and off-diagonal matrix elements of the Kohn-Sham Hamiltonian, respectively, for all possible combinations of nucleobases. Taking into account the Coulomb interaction between the negative charge on the stilbenedicarboxamide linker and the hole on the DNA strand as well as effects of base pair twisting, the relative order of the experimental rates for hole transfer in different hairpins could be reproduced by tight-binding calculations. To reproduce quantitatively the absolute values of the measured rate constants, the effect of the reorganization energy was taken into account within the semiclassical superexchange model for charge transfer. The experimental rates could be reproduced with reorganization energies near 1 eV. The quantum chemical data obtained were used to discuss charge carrier mobility and hole-transport equilibria in DNA.

Original languageEnglish (US)
Pages (from-to)14894-14903
Number of pages10
JournalJournal of the American Chemical Society
Issue number42
StatePublished - Nov 1 2005

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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