UV radiation creates excited states in DNA that lead to mutagenic photoproducts. Photoexcitation of single-stranded DNA can transfer an electron between stacked bases, but the fate of excited states in the double helix has been intensely debated. Here, photoinduced interstrand proton transfer (PT) triggered by intrastrand electron transfer (ET) is detected for the first time by time-resolved vibrational spectroscopy and quantum mechanical calculations. Long-lived excited states are shown to be oppositely charged base pair radical ions. In two of the duplexes, the base pair radical anions are present as tautomers formed by interstrand PT. Charge recombination occurs on the picosecond time scale preventing the accumulation of damaging radicals or mutagenic tautomers. © 2015 American Chemical Society.

*** IBB - CNR ***

Department of Chemistry and Biochemistry, Montana State University, Bozeman, MT, United States

Department of Physics, United States Air Force Academy, USAF AcademyCO, United States

Consiglio Nationale Delle Ricerche, Istituto di Biostrutture e Bioimmagini, Via Mezzocannone 16, Naples, Italy

daggerDepartment of Chemistry and Biochemistry, Montana State University, Bozeman, Montana 59717, United States., double daggerDepartment of Physics, United States Air Force Academy, USAF Academy, Colorado 80840, United States., section signConsiglio Nationale delle Ricerche, Istituto di Biostrutture e Bioimmagini, Via Mezzocannone 16, 80136 Naples, Italy.,

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