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DNA double‐helix‐mediated long‐range electron transfer
Author(s) -
Priyadarshy Satyam,
Beratan David N.,
Risser Steven M.
Publication year - 1996
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1996)60:8<1789::aid-qua6>3.0.co;2-u
Subject(s) - electron transfer , cndo/2 , chemistry , electron , range (aeronautics) , acceptor , atomic physics , marcus theory , coupling (piping) , chemical physics , molecular physics , molecule , reaction rate constant , kinetics , physics , materials science , condensed matter physics , quantum mechanics , organic chemistry , metallurgy , composite material
A theoretical analysis based upon large‐scale self‐consistent Hartree‐Fock calculations at a semiempirical quantum theory level (CNDO/S) is performed to investigate long‐range electron transfer in a donor‐DNA‐acceptor molecule, where the donor and acceptor moieties are tethered to the DNA. The π‐stacked base pairs are found to dominate the long‐range electronic coupling. Despite the π‐electron mediated coupling, the exponential distance decay constant of the electron transfer rate is ∼ 1.2–1.6 Å −1 , values typical of electron transfer proteins. The calculated long‐range electron transfer rate of the order of 10 6 s −1 for a metal‐to‐metal distance of 21 Å is found to be in agreement with kinetic measurements by Meade and Kayyem. Based on the current analysis, the π‐electrons dominate the long‐range electronic coupling interactions in DNA, but they do not lead to one‐dimensional molecular wire‐like properties. © 1996 John Wiley & Sons, Inc.