Understanding the Interplay Between the Non-Valence and Valence State of the Uracil Anion Upon Mono-Hydration

Cate S. Anstöter and Spiridoula Matsika, J. Phys. Chem. A, 2020, 124, 44, 9237-9243 (2020)

In this work we present an ab initio investigation into the effect of mono-hydration on the interaction of uracil with low energy electrons. Electron attachment and photodetachment experimental studies have previously shown dramatic changes in uracil upon solvation with even a single water molecule, due to an inversion of the character of the ground state of the anion. Here we explore the interplay between the non-valence and valence states of the uracil anion, as a function of geometry and site of solvation. Our model provides unambiguous interpretation of previous photoelectron studies, reproducing the binding energies and photoelectron images for bare uracil and a single isomer of the U•(H2O)1 cluster. The results of this study provide insight into how electrons may attach to hydrated nucleobases. These results lay the foundations for further investigations into the effect of micro-hydration on the electronic structure and dynamics of nucleobases.

URL: https://doi.org/10.1021/acs.jpca.0c07407