The structural evolution and electronic properties of TaSi_n^–/0 (n = 2–15) clusters are explored using anion photoelectron spectroscopy accompanied by quantum chemical calculations. The Ta atom in TaSi_n^–/0 is inclined to interact with more Si atoms and has high coordination numbers. The theoretical calculations show that TaSi₂^–/0 have trianglur structures and TaSi₃^–/0 adopt pyramid structures, while the geometries of TaSi_n^–/0 (n = 4–7) are all exohedral structures dominated by bipyramid-based configurations with the Ta atom face-capping the Si_n motifs. TaSi₈^–/0 and TaSi_9–10^– have boat-shaped geometries, whereas TaSi_9–10 neutrals adopt bipyramid-based geometries instead of boat-shaped ones. TaSi₁₁^– and TaSi₁₂ are confirmed as the critical size of transiting from exohedral to endohedral structures for anionic and neutral clusters, respectively. TaSi_12–15^–/0 have pentagonal or hexagonal prism-based geometries. Natural population analysis shows that the electron transfers from Si_n skeletons to Ta atom. The second-order energy differences (Δ₂E) and incremental binding energy (ΔE^I) values exhibit strong odd–even alternations, suggesting that the TaSi_n-odd^−/0 clusters are more stable than the adjacent TaSi_n-even^−/0 ones, except that TaSi_12^–/0 are more stable than TaSi_11^–/0 and TaSi_13^–/0.

中文翻译：

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TaSi _{n ^{– / 0}}（n = 2–15）团簇的结构演化和电子性质：尺寸选择的阴离子光电子能谱和理论计算

TaSi _{n ^{– / 0}}（n = 2–15）团簇的结构演变和电子性质是通过使用阴离子光电子能谱和量子化学计算来探索的。TaSi _{n ^{– / 0中}}的Ta原子倾向于与更多的Si原子相互作用，并具有较高的配位数。理论计算表明，TaSi ₂ ^{– / 0}具有三角结构，TaSi ₃ ^{– / 0}采用金字塔结构，而TaSi _n ^{– / 0}（n = 4–7）的几何结构都是双面体结构，主要由基于双锥体的构型和Ta原子覆盖Si _n图案。塔西₈ ^{– / 0}和TaSi _9–10 ^–具有船形几何形状，而TaSi _9–10中性线则采用基于双金字塔的几何形状而不是船形几何形状。的TaSi ₁₁ ^-和的TaSi ₁₂，确认为分别从exohedral过渡到富勒烯结构为阴离子和中性团簇，的临界尺寸。TaSi _12–15 ^{– / 0}具有基于五边形或六边形棱镜的几何形状。自然种群分析表明，电子从Si _n骨架转移到Ta原子。二阶能量差（Δ ₂ ë）和增量结合能（Δ Ë^我）值表现出强奇偶交替，这表明的TaSi _Ñ余^{- / 0}簇是比相邻的TaSi更稳定_{ñ -即使}^{- / 0}的，所不同的是的TaSi _{12 ^{- / 0}}是更稳定的比的TaSi _{11 ^{- / 0}}和TaSi _{13 ^{– / 0}}。