Computational study of interactions of the uracil molecule with the F- and [formula omitted] hard anions

Abstract

We report the first computational study on anion clusters of uracil with F- and O2-using the B3LYP, B3LYP-GD3 methods with the aug-cc-pVnZ basis sets, n = 2–5. In each cluster, the anion selectively abstracts a proton from a specific NH bond in uracil. The transferred proton forms an incipient chemical bond with the anion while the transferred proton becomes hydrogen bonded to the uracil moiety. Most of the anion’s negative charge is transferred to uracil while the electron-spin density is redistributed among the oxygen atoms in O2-. We identified two pathways for dissociation and vibrationally induced proton transfer within each complex. There are large red shifts in frequencies and massive increase in intensities of the IR stretches in the protonated anions within the clusters. These new findings advance our knowledge about interactions of O2-with nucleotide bases and provide predictions for IR spectroscopic detection of the O2- uracil cluster.