Role of the Hydrogen Bond on the Internal Conversion of Photoexcited Adenosine

Experiments and theory have revealed that hydrogen bonds modify the excited-state lifetimes of nucleosides compared to nucleobases. Nevertheless, how these bonds impact the internal conversion is still unsettled. This work simulates the non-adiabatic dynamics of adenosine conformers in the gas phase with and without hydrogen bonds between the sugar and adenine moieties. The isomer containing the hydrogen bond (syn) exhibits a significantly shorter excited-state lifetime than the isomer without it (anti). However, internal conversion through electron-driven proton transfer between sugar and adenine plays only a minor (although non-negligible) role in the photophysics of adenosine. Either with or without hydrogen bonds, photodeactivation preferentially occurs following the ring-puckering pathways. The role of the hydrogen bond is to avoid the sugar rotation relative to adenine, shortening the distance to the ring-puckering internal conversion.