First-principles GW calculations for DNA and RNA nucleobases

Abstract

On the basis of first-principles GW calculations, we study the quasiparticle properties of the guanine, adenine, cytosine, thymine, and uracil DNA and RNA nucleobases. Beyond standard G0W0 calculations, starting from Kohn-Sham eigenstates obtained with (semi)local functionals, a simple self-consistency on the eigenvalues allows to obtain vertical ionization energies and electron affinities within an average 0.11 eV and 0.18 eV error respectively as compared to state-of-the-art coupled-cluster and multi-configurational perturbative quantum chemistry approaches. Further, GW calculations predict the correct \pi -character of the highest occupied state, thanks to several level crossings between density functional and GW calculations. Our study is based on a recent gaussian-basis implementation of GW with explicit treatment of dynamical screening through contour deformation techniques.Comment: 5 pages, 3 figure