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

结合重整化单粒子引力波方法和贝特-萨尔佩特方程计算精确的中性激发能

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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(RS)W(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(RS)W(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(RS)W(RS) provides comparable accuracy to time-dependent density functional theory (TDDFT) and is slightly better than BSE starting from eigenvalue self-consistent GW (evGW). For the Stein CT test set, BSE/G(RS)W(RS) significantly outperforms BSE/G(0)W(0) and TDDFT with the accuracy comparable to BSE/evGW. We also show that BSE/G(RS)W(RS) predicts Rydberg excitation energies of atomic systems well. Besides the excellent accuracy, BSE/G(RS)W(RS) largely eliminates the dependence on the choice of the density functional approximation. This work demonstrates that the BSE/G(RS)W(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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