Summary

Abstract(#br)Adenosine radicals tagged with a fixed‐charge group were generated in the gas phase and structurally characterized by tandem mass spectrometry, deuterium labeling, and UV/Vis action spectroscopy. Experimental results in combination with Born–Oppenheimer molecular dynamics, ab initio, and excited‐state calculations led to unambiguous assignment of adenosine radicals as N‐ hydrogen atom adducts. The charge‐ agged radicals were found to be electronically equivalent to natural DNA nucleoside radicals.

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