Electron Affinities of Small Uracil−Water Complexes: A Comparison of Benchmark CCSD(T) Calculations with DFT

Abstract

We present benchmark CCSD(T) calculations of the adiabatic electron affinities (AEA) and the vertical detachment energies (VDE) of the uracil molecule interacting with one to three water molecules. Calculations with rather large aug-cc-pVTZ basis set were only tractable when the space of virtual orbitals was reduced to about 60% of the full space employing the OVOS (Optimized Virtual Orbital Space) technique. Because of the microhydration, the valence-bound uracil anion is stabilized leading to gradually more positive values of both AEA and VDE with increasing number of participating water molecules. This agrees with experimental findings. Upon hydration by three water molecules, the electron affinity of uracil increased in comparison with AEA of the isolated molecule by about 250 up to 570 meV, depending on the geometry of the complex. CCSD(T) results confirm trends determined by DFT calculations of the microhydrated uracil and its anion, even if electron affinities of the free and hydrated uracil molecule are overestimated by DFT by up to 300 meV.