The geometrical structures, electron leading configurations, and relative energies of the low‐lying states of VGe n−/0 (n = 5–7) clusters have been investigated with density functional theory and CASSCF/CASPT2 method. The pure GGA BP86 functional gave almost the same relative energy order for the low‐lying states as the CASPT2 method. At the BP86 and CASPT2 levels, the ground states of VGe n−/0 (n = 5–7) clusters were proposed to be the 1A1 and 2A1 of A‐VGe5−/0, 3A″ and 2A″, 2A′ (2E2) of A‐VGe6−/0, and 1A′ and 2A′ of A‐VGe7−/0 isomers. The adiabatic and vertical detachment energies (ADEs and VDEs) of the detachments of one electron from several orbitals of the anionic ground states were reported at the CASPT2 level. The calculated ADEs and VDEs corresponded well with the experimental values as observed in the 266 nm anion photoelectron spectra. © 2018 Wiley Periodicals, Inc.

中文翻译：

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VGe n -/0 (n = 5-7) 簇的自旋态能量学和阴离子光电子谱的新分配

已经使用密度泛函理论和 CASSCF/CASPT2 方法研究了 VGe n-/0 (n = 5-7) 团簇的低位态的几何结构、电子引导配置和相对能量。纯 GGA BP86 泛函给出了与 CASPT2 方法几乎相同的低洼状态的相对能量阶数。在 BP86 和 CASPT2 能级，VGe n-/0 (n = 5-7) 簇的基态被提议为 A-VGe5-/0, 3A" 和 2A", 2A' (2E2) 的 1A1 和 2A1 ) A-VGe6-/0 和 A-VGe7-/0 异构体的 1A' 和 2A'。一个电子从阴离子基态的几个轨道脱离的绝热和垂直脱离能（ADE 和 VDE）在 CASPT2 水平上报告。计算出的 ADE 和 VDE 与在 266 nm 阴离子光电子光谱中观察到的实验值非常吻合。