Electron Attachment to Solvated dGpdG: Effects of Stacking on Base‐Centered and Phosphate‐Centered Valence‐Bound Radical Anions

To explore the nature of electron attachment to guanine‐centered DNA single strands in the presence of a polarizable medium, a theoretical investigation of the DNA oligomer dinucleoside phosphate deoxyguanylyl‐3′,5′‐deoxyguanosine (dGpdG) was performed by using density functional theory. Four different electron‐distribution patterns for the radical anions of dGpdG in aqueous solution have been located as local minima on the potential energy surface. The excess electron is found to reside on the proton of the phosphate group (dGp^H?dG), or on the phosphate group (dGp^.?dG), or on the nucleobase at the 5′ position (dG^.?pdG), or on the nucleobase at the 3′ position (dGpdG^.?), respectively. These four radical anions are all expected to be electronically viable species under the influence of the polarizable medium. The predicted energetics of the radical anions follows the order dGp^.?dG>dG^.?pdG>dGpdG^.?>dGp^H?dG. The base–base stacking pattern in DNA single strands seems unaffected by electron attachment. On the contrary, intrastrand H‐bonding is greatly influenced by electron attachment, especially in the formation of base‐centered radical anions. The intrastrand H‐bonding patterns revealed in this study also suggest that intrastrand proton transfer might be possible between successive guanines due to electron attachment to DNA single strands.