The global minima of both neutral and anionic clusters of VGe₃^–/0 were determined using different quantum chemical methods (DFT, RCCSD(T), CASSCF/CASPT2). On the basis of the ground states identified, most excited bands in the anion photoelectron spectrum of VGe₃^– were assigned. The tetrahedral isomers of both charged states are the most stable ones. A singlet state (C_s ^, 1A′) of the tetrahedral isomer has the globally lowest energy on the potential hypersurface of VGe₃^–. Two states 1²A′ and 1²A″ of the neutral tetrahedral isomer are nearly degenerate and identified as the competing ground state of VGe₃. From the anionic ground state, four of five bands in the anion photoelectron spectrum of VGe₃^– were determined to be the consequences of one-electron transitions starting from the anionic ground state ¹A′. Both nearly degenerate neutral ground states are responsible for generation of the first band. Two different transitions from the anionic ground state ¹A′ to the first two nearly degenerate excited states (2²A′ and 2²A″) of the neutral underlie the second lowest ionization band. Two higher levels of ionization recorded in the spectrum were assigned to the two higher excited states 4²A′ and 5²A′ of the neutral. Franck–Condon factor simulations of the first band were performed to obtain more insights into the experimental bands of the spectrum.

中文翻译：

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从阴离子光电子谱分配洞察VGe ₃ ^{– / 0}团簇的几何和电子结构

使用不同的量子化学方法（DFT，RCCCD（T），CASSCF / CASPT2）确定了VGe _3- ^{/ 0的}中性和阴离子簇的全局最小值。根据确定的基态，分配了VGe ₃ ^–的阴离子光电子能谱中的大多数激发能带。两种带电态的四面体异构体是最稳定的。四面体异构体的单重态（C _s ^，1 A'）在VGe ₃ ^–的潜在超表面上具有全球最低的能量。两个状态1 ² A'和1名² A“的中性四面体的异构体几乎退化并鉴定为VGE的竞争基态₃。根据阴离子基态，确定VGe ₃ ^–的阴离子光电子能谱中的五个能带中的四个是从阴离子基态¹ A'开始的单电子跃迁的结果。两种几乎退化的中性基态都负责生成第一频带。从阴离子基态¹ A'到中性的前两个简并的激发态（2 ² A'和2 ² A '' ）的两个不同跃迁位于第二最低电离带之下。光谱中记录的两个较高的电离水平被分配给两个较高的激发态4 ² A'和5 ²中性的A'。对第一个谱带进行Franck–Condon因子模拟，以获得对光谱实验谱带的更多见解。