采用CCSD(T)/aug-cc-pVTZ-DK//MP2/6-31G(2df, p)和B3LYP/ aug-cc-pVTZ基组研究了小尺寸团簇CrSin (n=3~9)及其阴离子的结构、 稳定性以及光电子谱。 结果表明: 中性及其阴离子的基态结构是外嵌结构。 由计算得出的解离能可知, 在n<5时, CrSin中性结构的稳定性弱于其阴离子结构。 在n≥5时, CrSin中性结构中, CrSi5和CrSi8结构的稳定性强于其相邻团簇; CrSin阴离子结构中, CrSi4和CrSi7结构的稳定性弱于其相邻团簇。 计算得出的CrSin垂直电子解离能分别为: CrSi3 (2.26 eV), CrSi4 (3.21 eV), CrSi5 (2.72 eV), CrSi6 (3.54 eV), CrSi7 (2.45 eV), CrSi8 (2.71 eV)和CrSi9 (2.95 eV)。 除CrSi4以外, 其他CrSin结构的垂直电子解离能数值与实验值很好符合, 平均绝对误差仅为0.073 eV。 计算得出的CrSin绝热电子亲和能分别为: CrSi3 (2.07 eV), CrSi4 (1.95 eV), CrSi5 (2.4 eV), CrSi6 (2.32 eV), CrSi7 (2.38 eV), CrSi8 (2.67 eV)和CrSi9 (2.63 eV)。 除CrSi6以外, 其他CrSin结构的绝热电子亲和能与实验值很好符合, 平均绝对误差仅为0.09 eV。 此外, 在PBE1PBE/6-31G(2df, p)水平下模拟了CrSin (n=3～9)阴离子基态结构的光电子光谱, 并与报道的实验结果相比较, 可以得出该研究得到的基态结构是可靠的。

The structures, stability and spectroscopic property of Chromium doped small silicon clusters CrSin (n=3～9) and their anions are systematically investigated using CCSD(T)/aug-cc-pVTZ-DK//MP2/6-31G(2df, p) and the B3LYP/ aug-cc-pVTZ basis set. The results show that the ground-state structures of neutral CrSin (n=3～9) and their anion are all exohedral structures. According to the calculated dissociation energies, it shows that when n<5, the neutral CrSin are less stable than their anion. And when n≥5, the CrSi5 and CrSi8 of neutral CrSin are more stable than their neighboring clusters; the CrSi4 and CrSi7 of anionic CrSin are less stable than their neighboring clusters. The VDEs of CrSin are predicted to be 2.26 eV for CrSi3, 3.21 eV for CrSi4, 2.72 eV for CrSi5, 3.54 eV for CrSi6, 2.45 eV for CrSi7, 2.71 eV for CrSi8 and 2.95 eV for CrSi9. They are in excellent agreement with experimental data except for CrSi4, the average absolute deviations from experimental data are only 0.073 eV. The AEAs of CrSin are evaluated to be 2.07 eV for CrSi3, 1.95 eV for CrSi4, 2.4 eV for CrSi5, 2.32 eV for CrSi6, 2.38 eV for CrSi7, 2.67 eV for CrSi8, and 2.63 eV for CrSi9. Except for CrSi6, they are in excellent agreement with experimental data. The average absolute deviations from experimental data are only 0.09 eV. Besides, the photoelectron spectra (PES) of ground-state structures of anionic CrSin (n=3～9) are simulated at the PBE1PBE/6-31G(2df, p) level, and compared to the corresponding experiment data, it is concluded that the ground-state structures obtained in this paper are reliable.