第一过渡系金属水合离子的$G_0W_0$电离能
$G_0W_0$ Ionization Potentials of First-Row Transition Metal Aqua Ions
AI总结：
本研究采用$G_0W_0$方法计算第一过渡系常见氧化态水合离子的垂直电离能，评估不同基组、水分子团簇尺寸和起始密度泛函的影响，发现r2SCAN基的方法兼顾精度与计算效率，结果与实验吻合良好。
摘要：
我们报道了采用$GW$近似计算的、近完整系列第一过渡系（钒-铜）水合离子在其最常见氧化态下的垂直电离能，涉及的离子包括V$^{3+}$、Cr$^{3+}$、Cr$^{2+}$、Mn$^{2+}$、Fe$^{3+}$、Fe$^{2+}$、Co$^{2+}$、Ni$^{2+}$和Cu$^{2+}$。这些体系的$d$轨道占据数覆盖了从$d^2$到$d^9$的宽泛范围。所有结构首先在密度泛函理论水平下进行优化，采用嵌入连续溶剂化模型的大尺寸显式水分子团簇。我们使用单次$G_0W_0$方法计算了一系列过渡金属离子团簇（含6、18、40和60个显式水分子）的垂直电离能，并针对含40个水分子的体系评估了基组尺寸的收敛性。我们采用三种不同的密度泛函近似作为垂直电离能计算的起点来评估结果，分别为$G_0W_0$@PBE、$G_0W_0$@PBE0和$G_0W_0$@r$^2$SCAN。尽管三种交换关联泛函预测的基态结构相近，但使用$G_0W_0$@PBE0和$G_0W_0$@r$^2$SCAN方法得到的垂直电离能与实验结果更吻合，其中基于r2SCAN的计算成本显著更低。所有结构的计算键长和垂直电离能均与现有实验数据进行了比较，二者吻合良好。
英文摘要：
We report computations of the vertical ionization potentials within the $GW$ approximation of the near-complete series of first-row transition metal (V-Cu) aqua ions in their most common oxidation states, i.e. V$^{3+}$, Cr$^{3+}$, Cr$^{2+}$, Mn$^{2+}$, Fe$^{3+}$, Fe$^{2+}$, Co$^{2+}$, Ni$^{2+}$, and Cu$^{2+}$. The $d$-orbital occupancy of these systems spans a broad range from $d^2$ to $d^9$. All the structures were first optimized at the density functional theory level using a large cluster of explicit water molecules that are embedded in a continuum solvation model. Vertical ionization potentials were computed with the one-shot $G_0W_0$ approach on a range of transition metal ion clusters (6, 18, 40, and 60 explicit water molecules) wherein the convergence with respect to the basis set size was evaluated using the systems with 40 water molecules. We assess the results using three different density functional approximations as starting points for the vertical ionization potential calculations, namely $G_0W_0$@PBE, $G_0W_0$@PBE0, and $G_0W_0$@r$^2$SCAN. While the predicted ground-state structures are similar with all three exchange-correlation functionals, the vertical ionization potentials were in closer agreement with the experiment when using the $G_0W_0$@PBE0 and $G_0W_0$@r$^2$SCAN approaches, with the r2SCAN based calculations being significantly less expensive. Computed bond distances and vertical ionization potentials for all structures were compared with available experimental data and are in good agreement.
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