论文标题
顶点效应在描述第一行过渡金属一氧化物分子的电离能
Vertex effects in describing the ionization energies of the first-row transition-metal monoxide molecules
论文作者
论文摘要
$ GW $近似被认为是Hedin的多体扰动理论的最简单近似值。预计可以通过添加所谓的顶点校正来克服$ GW $近似的某些缺陷。在这项工作中，最近实现的$G_0W_0γ^{（1）} _ 0 $方案，该方案通过将完整的二阶自我能源校正添加到$ GW $自我能源中，将顶点效应纳入了顶点效果，适用于一组第一行过渡 - 一氧化合物（TMO）肛门。基准计算表明，由$g_0w_0γ^{（1）} _ 0 $获得的结果在B3Lyp混合功能起点（SP）之上与实验数据非常吻合，给出了由27个外瓦尔卡（MOS）的电离能量（IES）的平均绝对误差为0.13 eV（IES），该测试集的平均绝对误差（IES）。通过改变PBE0型SP中精确交换（EXX）组件的比率的系统依赖性研究表明，对于$G_0W_0γ^{（1）} _ 0 $，可以使用20美元的$ 20 \％$ exx实现最佳准确性。 Further error analysis in terms of the orbital symmetry characteristics (i.e, $σ$, $π$, or $δ$) in the testset indicate the best amount of EXX in the SP for $G_0W_0Γ^{(1)}_0$ calculations is independent of MO types, and this is in contrast with the situation of $G_0W_0$ calculations where the best EXX ratio varies for different classes of MOs.尽管它成功地描述了绝对IE值，但我们发现$g_0w_0γ^{（1）} _ 0 $在描述某些感兴趣的某些感兴趣状态之间的能量分离方面遇到困难，从而使已经被低估的$ G_0W_0 $预测更加恶化。
The $GW$ approximation is considered to be the simplest approximation with Hedin's formulation of many-body perturbation theory. It is expected that some of the deficiencies of the $GW$ approximation can be overcome by adding the so-called vertex corrections. In this work, the recently implemented $G_0W_0Γ^{(1)}_0$ scheme, which incorporates the vertex effects by adding the full second-order self-energy correction to the $GW$ self-energy, is applied to a set of first-row transition-metal monoxide (TMO) anions. Benchmark calculations show that results obtained by $G_0W_0Γ^{(1)}_0$ on top of the B3LYP hybrid functional starting point (SP) are in good agreement with experiment data, giving a mean absolute error of 0.13 eV for a testset comprising the ionization energies (IEs) of 27 outer valence molecular orbitals (MOs) from 9 TMO anions. A systematic SP-dependence investigation by varying the ratio of the exact exchange (EXX) component in the PBE0-type SP reveals that, for $G_0W_0Γ^{(1)}_0$, the best accuracy is achieved with $20\%$ EXX. Further error analysis in terms of the orbital symmetry characteristics (i.e, $σ$, $π$, or $δ$) in the testset indicate the best amount of EXX in the SP for $G_0W_0Γ^{(1)}_0$ calculations is independent of MO types, and this is in contrast with the situation of $G_0W_0$ calculations where the best EXX ratio varies for different classes of MOs. Despite its success in describing the absolute IE values, we however found that $G_0W_0Γ^{(1)}_0$ faces difficulties in describing the energy separations between certain states of interest, worsening the already underestimated $G_0W_0$ predictions.
