TOWARD THE MECHANISM OF LONG-RANGE CHARGE TRANSFER IN DNA: THEORIES AND MODELS

Abstract

This article reviews our recent theoretical development toward understanding the interplay of electronic structure and dephasing effects on charge transfer/transport through molecular donor-bridge-acceptor systems. Both the generalized scattering matrix and Green's function formalisms for partially incoherent tunneling processes are summarized. Presented is also an exact mapping between the kinetic rate constants and the electric conductances in evaluation of chemical yields of sequential charge transfer in the presence of competing branching reactions. As an important example, the mechanism of long-range charge transfer in DNA in aqueous solution is investigated with a quantum chemistry implementation of the generalized Green's function formalism. A time scale of about 5 ps is found for the partially incoherent tunneling through a thymine/adenine π-stack in DNA. Numerical results further show that while the carrier oxidative charge does hop sequentially over all guanine sites in a DNA duplex, its tunneling over thymine/adenine bridge base pairs deviates substantially from the superexchange regime. Presented are also evidences for the involvement of both intrastrand and interstrand pathways in the ground state hole charge transfer in DNA.