Water mediated electron attachment to nucleobases: Surface-bound vs bulk solvated electrons

Abstract

We have presented a mechanism for electron attachment to solvated nucleobases using accurate wave-function based hybrid quantum/classical (QM/MM) simulations and uracil as a test case. The initial electron attached state is found to be localized in the bulk water, and this water-bound state acts as a doorway to the formation of the final nucleobase bound state. The electron transfer from water to uracil takes place because of the mixing of electronic and nuclear degrees of freedom. The water molecules around the uracil stabilize the uracil-bound anion by creating an extensive hydrogen-bonding network and accelerate the rate of electron attachment to uracil. The complete transfer of the electron from water to the uracil occurs in a picosecond time scale, which is consistent with the experimentally observed rate of reduction of nucleobases in the presence of water. The degree of solvation of the aqueous electron can lead to a difference in the initial stabilization of the uracil-bound anion. However, the anions formed due to the attachment of both surface-bound and bulk-solvated electrons behave similarly to each other at a longer time scale.