论文标题
来自$ GW $
Relativistic correction scheme for core-level binding energies from $GW$
论文作者
论文摘要
我们提出了一种相对论校正方案，以提高根据$ GW $近似中格林的功能理论计算出的1S核心级结合能的准确性，该函数理论不会添加计算开销。特定于元素的纠正术语被得出作为从非或标量与标量的kohn-sham方程和四组分dirac-kohn-sham方程的1S特征值之间的差异。我们检查了该纠正术语对分子环境的依赖性以及混合交换相关功能中的精确交换量。然后将此纠正术语添加为对Quasiparticle能量的扰动。我们表明，当应用于先前报道的65个核心状态激发的基准集时，这种元素特异性的相对论校正[J.物理。化学Lett。 11，1840（2020）]，将实验的平均绝对误差（MAE）从0.55到0.30 eV减少，并消除了MAE的物种依赖性，否则随着原子数而增加。相对论校正还减少了物种的依赖性，以作为单发$ G_0W_0 $计算的混合功能中最佳的精确交换量。我们的校正方案可以转移到其他方法中，我们根据密度功能理论为三角洲自洽场（$δ$ scf）方法证明了这一点。
We present a relativistic correction scheme to improve the accuracy of 1s core-level binding energies calculated from Green's function theory in the $GW$ approximation, which does not add computational overhead. An element-specific corrective term is derived as the difference between the 1s eigenvalues obtained from the self-consistent solutions to the non- or scalar-relativistic Kohn-Sham equations and the four-component Dirac-Kohn-Sham equations for a free neutral atom. We examine the dependence of this corrective term on the molecular environment and on the amount of exact exchange in hybrid exchange-correlation functionals. This corrective term is then added as a perturbation to the quasiparticle energies from partially self-consistent and single-shot $GW$ calculations. We show that this element-specific relativistic correction, when applied to a previously reported benchmark set of 65 core-state excitations [J. Phys. Chem. Lett. 11, 1840 (2020)], reduces the mean absolute error (MAE) with respect to experiment from 0.55 to 0.30 eV and eliminates the species dependence of the MAE, which otherwise increases with the atomic number. The relativistic corrections also reduce the species dependence for the optimal amount of exact exchange in the hybrid functional used as starting point for the single-shot $G_0W_0$ calculations. Our correction scheme can be transferred to other methods, which we demonstrate for the Delta self-consistent field ($Δ$SCF) approach based on density functional theory.
