The geometrical and electronic structures of the low-lying states of VSi₄^−/0 clusters as computed with the density functional theory and the multiconfigurational CASSCF/CASPT2 method are reported. The results show that the appropriate functionals to investigate the VSi₄^−/0 clusters are the pure GGA BP86 and PBE functionals, while the hybrid B3LYP and PBE0 functionals underestimate the energies of the high-spin states. All features in the photoelectron spectrum of VSi₄⁻ cluster are interpreted based on the one-electron detachments from the ¹A′ of trigonal bipyramid VSi₄⁻ isomer in which the V atom is distributed in the equatorial corner of the bipyramid.

中文翻译：

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VSI的光电子能谱的新解读₄ ^-簇的密度泛函理论和Multiconfigurational CASSCF / CASPT2计算

报道了利用密度泛函理论和多构型CASSCF / CASPT2方法计算的VSi _4- ^{/ 0}团簇低态的几何和电子结构。结果表明，研究VSi _4- ^{/ 0}簇的合适功能是纯GGA BP86和PBE功能，而混合B3LYP和PBE0功能低估了高自旋态的能量。在VSI的光电子能谱所有功能₄ ^-集群是基于解释的单电子分队从^1个三角双锥VSI的A' ₄ ^-异构体，其中在V原子分布在双锥的赤道角。