Abstract
The anion radical of the 2′-deoxyadenosine···thymine (dAT•–) pair has been investigated experimentally and theoretically in the gas phase. By employing negative-ion photoelectron spectroscopy (PES), we have registered a spectrum typical for the valence-bound anion, featuring a broad peak at the electron-binding energy (EBE) between ∼1.5 and 2.2 eV with the maximum at ∼1.9 eV. The measured value of the adiabatic electron affinity (AEA) for dAT was estimated to be ∼1.1 eV. Calculations performed at the M06-2X/6-31++G(d,p) level revealed that the structure, where thymine is coordinated to the sugar of dA by two hydrogen bonds, is responsible for the observed PES signal. The AEAG and the vertical detachment energy of 0.91 and 1.68 eV, respectively, calculated for this structure reproduce the experimental values well. The role of the possible proton transfer in the stabilization of anionic radical complexes is discussed.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a call
