论文标题
$ \ boldsymbol {gw} $方法的核心级绑定能量的基准
Benchmark of $\boldsymbol{GW}$ Methods for Core-Level Binding Energies
论文作者
论文摘要
$ GW $近似最近已获得越来越多的关注，作为一种可行的方法，用于计算通过X射线光电子光谱（XPS）测量的深核水平结合能。我们介绍了针对分子内壳激发的不同$ GW $方法的全面基准研究（起点优化，部分优化，部分和完整的特征值一致，Hedin Shift和Rentormization Singles）。我们证明所有方法都会产生独特的解决方案，并将其应用于Core65基准组和三氟乙酸乙酯。相对于实验，三个$ GW $方案显然超过了其他方法的绝对核心水平能量的其他方法为0.3 eV。这些是部分特征值自隔离性，其中特征值仅在绿色的功能中更新，基于优化的混合功能起点和绿色功能的Hedin Shift在Green的功能中进行了$ GW $计算。尽管所有方法都很好地重现了实验性相对结合能，但特征值自一致方案和Hedin Shings屈服的平均误差$ <0.2 $ ev是最佳结果。
The $GW$ approximation has recently gained increasing attention as a viable method for the computation of deep core-level binding energies as measured by X-ray photoelectron spectroscopy (XPS). We present a comprehensive benchmark study of different $GW$ methodologies (starting-point optimized, partial and full eigenvalue-self-consistent, Hedin shift and renormalized singles) for molecular inner-shell excitations. We demonstrate that all methods yield a unique solution and apply them to the CORE65 benchmark set and ethyl trifluoroacetate. Three $GW$ schemes clearly outperform the other methods for absolute core-level energies with a mean absolute error of 0.3 eV with respect to experiment. These are partial eigenvalue self-consistency, in which the eigenvalues are only updated in the Green's function, single-shot $GW$ calculations based on an optimized hybrid functional starting point and a Hedin shift in the Green's function. While all methods reproduce the experimental relative binding energies well, the eigenvalue self-consistent schemes and the Hedin shift yield with mean errors $<0.2$ eV the best results.
