Screening mixing GW/Bethe–Salpeter approach for triplet states of organic molecules

Abstract

We recently proposed a screening mixing many-body ansatz (Ziaei and Bredow 2017 Phys. Rev. B 96 195115) to decrease the typical overestimation of the Hartree–Fock based GW/Bethe–Salpeter equation (BSE) singlet–singlet excitation energies in molecular systems. Now we have evaluated the accuracy of the proposed scheme for triplet states of a set of 20 organic molecules known as the Thiel set. We show that by mixing different screenings into GW and BSE calculated within random phase approximation (in order to ensure best gap and an optimal exciton binding energy), the total mean absolute error of 0.59 eV in the standard Hartree–Fock based eigenvalue GW/BSE approach is reduced to 0.26 eV for 63 triplet states. We further demonstrate that the quasi-particle self-consistent GW/BSE approach in which orbitals and energies are updated in the Green’s function and the dynamically screened interaction mostly and considerably underestimates the excitation energies as shown for a few molecules.