PNNL

Abstract

A series of eighteen alcohols (ROH) has been designed with an enthalpy of deprotonation (HDP) in a range of 13.8-16.3 eV. The effects of excess electron attachment to the binary alcohol-uracil (ROH…U) complexes have been studied at the density functional level with a B3LYP exchange-correlation functional and at the second order Møller-Plesset perturbation theory level. The photoelectron spectra of anionic complexes of uracil with three alcohols (ethanol, 2,2,3,3,3-pentafluoroethanol and 1,1,1,3,3,3-hexafluoro-2-propanol) have been measured with 2.54 eV photons. For ROHs with deprotonation enthalpies larger than 14.8 eV only the ROH...U- minimum exists on the potential energy surface of the anionic complex. For alcohols with deprotonation enthalpies in a range of 14.3-14.8 eV two minima might exist on the anionic potential energy surface, which correspond to the RO-…HU. and ROH...U- structures. For ROHs with deprotonation enthalpies smaller than 14.3 eV, the excess electron attachment to the ROH…U complex always induces a barrier-free proton transfer from the hydroxyl group of ROH to the O8 atom of U, with the product being RO-…HU.. A driving force for the intermolecular proton transfer is to stabilize the excess negative charge localized on a ?* orbital of uracil. Therefore, these complexes with proton transferred to the anionic uracil are characterized by larger values of electron vertical detachment energy (VDE). The values of VDE for anionic complexes span a range from 1.0 to 2.3 eV and roughly correlate with the acidity of alcohols. However, there is a gap of ~0.5 eV in the values of VDE, which separates the two families, ROH...U- and RO-…HU., of anionic complexes. The energy of stabilization for the anionic complexes spans a range from 0.6 to 1.7 eV and roughly correlates with the acidity of alcohols. The measured photoelectron spectra are in good agreement with the theoretical predictions.