INAUGURAL ARTICLE by a Recently Elected Academy Member:Charge transfer and transport in DNA

We explore charge migration in DNA, advancing two distinct mechanisms of charge separation in a donor (d)–bridge ({B_j})–acceptor (a) system, where {B_j} = B₁,B₂,… , B_N are the N-specific adjacent bases of B-DNA: (i) two-center unistep superexchange induced charge transfer, d*{B_j}a → d{B_j}a^±, and (ii) multistep charge transport involves charge injection from d* (or d⁺) to {B_j}, charge hopping within {B_j}, and charge trapping by a. For off-resonance coupling, mechanism i prevails with the charge separation rate and yield exhibiting an exponential dependence exp(−βR) on the d-a distance (R). Resonance coupling results in mechanism ii with the charge separation lifetime τ N^η and yield Y (1 + N^η)⁻¹ exhibiting a weak (algebraic) N and distance dependence. The power parameter η is determined by charge hopping random walk. Energetic control of the charge migration mechanism is exerted by the energetics of the ion pair state dB₁^±B₂… B_Na relative to the electronically excited donor doorway state d*B₁B₂… B_Na. The realization of charge separation via superexchange or hopping is determined by the base sequence within the bridge. Our energetic–dynamic relations, in conjunction with the energetic data for d*/d⁻ and for B/B⁺, determine the realization of the two distinct mechanisms in different hole donor systems, establishing the conditions for “chemistry at a distance” after charge transport in DNA. The energetic control of the charge migration mechanisms attained by the sequence specificity of the bridge is universal for large molecular-scale systems, for proteins, and for DNA.