First-principlesGWcalculations 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 ${G}_{0}{W}_{0}$ calculations, starting from Kohn-Sham eigenstates obtained with (semi)local functionals, a simple self-consistency on the eigenvalues allows us to obtain vertical ionization energies and electron affinities within an average 0.11 and 0.18 eV error, respectively, as compared to state-of-the-art coupled-cluster and multiconfigurational perturbative quantum chemistry approaches. Further, GW calculations predict the correct $\ensuremath{\pi}$-character of the highest occupied state, due to several level crossings between density functional and GW calculations. Our study is based on a recent Gaussian-basis implementation of GW calculations with explicit treatment of dynamical screening through contour deformation techniques.