Combining Renormalized Singles GW Methods with the Bethe-Salpeter Equation for Accurate Neutral Excitation Energies.
Combining Renormalized Singles GW Methods with the Bethe-Salpeter Equation for Accurate Neutral Excitation Energies.
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DOI：
10.1021/acs.jctc.2c00686
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发表时间：
2022-06
影响因子：
5.5
通讯作者：
Jiachen Li;Dorothea Golze;Weitao Yang
中科院分区：
文献类型：
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作者：
Jiachen Li;Dorothea Golze;Weitao Yang
我们在Bethe-Salpeter方程(BSE)/GW方法中应用重整化的单峰(RS)格林函数来精确预测分子体系的中性激发能。BSE的计算是在GRSWRS方法的基础上进行的，GRSWRS方法也使用RS格林函数来计算屏蔽库仑相互作用W。通过比较TruhlarGagliardi集、Stein CT集和原子Rydberg测试集，BSE/GRSWRS方法在预测价激发、里德堡激发和电荷转移(CT)激发能方面明显优于BSE/G0W0。对于TruhlarGagliardi测试集，BSE/GRSWRS提供了与时间相关密度泛函理论(TDDFT)相当的精度，略好于从特征值自洽GW(EvGW)开始的BSE。对于Stein CT测试集，BSE/GRSWRS的性能明显优于BSE/G0W0和TDDFT，其精度与BSE/evGW相当。BSE/GRSWRS能很好地预测原子系统的里德堡激发能。除了良好的精度外，BSE/GRSWRS在很大程度上消除了对密度泛函近似选择的依赖。结果表明，BSE/GRSWRS方法能准确有效地预测大范围系统的激发能，扩展了BSE/GW方法的适用范围。
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 GRSWRS method, which uses the RS Green's function also for the computation of the screened Coulomb interaction W. We show that the BSE/GRSWRS approach significantly outperforms BSE/G0W0 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/GRSWRS 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/GRSWRS significantly outperforms BSE/G0W0 and TDDFT with the accuracy comparable to BSE/evGW. We also show that BSE/GRSWRS predicts Rydberg excitation energies of atomic systems well. Besides the excellent accuracy, BSE/GRSWRS largely eliminates the dependence on the choice of the density functional approximation. This work demonstrates that the BSE/GRSWRS approach is accurate and efficient for predicting excitation energies for a broad range of systems, which expands the applicability of the BSE/GW approach.