Combining Renormalized Singles $GW$ Methods with the Bethe-Salpeter Equation for Accurate Neutral Excitation Energies

Abstract

We apply the renormalized singles (RS) Green's function in the Bethe-Salpeter equation (BSE)/$GW$ approach to predict accurate neutral excitation energies of molecular systems. The BSE calculations are performed on top of the $G_{\text{RS}}{W}_{\text{RS}}$ method, which uses the RS Green's function also for the computation of the screened Coulomb interaction $W$. We show that the BSE/$G_{\text{RS}}{W}_{\text{RS}}$ approach significantly outperforms BSE/$G_0{W}_0$ for predicting excitation energies of valence, Rydberg and charge transfer (CT) excitations by benchmarking the Truhlar-Gagliardi set, Stein CT set and an atomic Rydberg test set. For the Truhlar-Gagliardi test set, BSE/$G_{\text{RS}}{W}_{\text{RS}}$ provides comparable accuracy to time-dependent density functional theory (TDDFT) and is slightly better than BSE starting from eigenvalue self-consistent $GW$ (ev$GW$). For the Stein CT test set, BSE/$G_{\text{RS}}{W}_{\text{RS}}$ significantly outperforms BSE/$G_0{W}_0$ and TDDFT with the accuracy comparable to BSE/ev$GW$. We also show that BSE/$G_{\text{RS}}{W}_{\text{RS}}$ predicts Rydberg excitation energies of atomic systems well. Besides the excellent accuracy, BSE/$G_{\text{RS}}{W}_{\text{RS}}$ largely eliminates the dependence on the choice of the density functional approximation. This work demonstrates that the BSE/$G_{\text{RS}}{W}_{\text{RS}}$ approach is accurate and efficient for predicting excitation energies for a broad range of systems, which expands the applicability of the BSE/$GW$ approach.

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