随着硅团簇研究的深入，过渡金属原子掺杂硅团簇的研究得到广泛关注。基于密度泛函理论，系统分析了钒原子掺杂硅团簇的几何结构、稳定性及特性。首先，基于粒子群优化算法的卡里普索结构预测程序，对V2Sin-/0(n=8~17)团簇的基态和亚稳态结构进行了系统搜索。B3LYP/6-311+G(d)水平下优化发现，基态结构中2个钒原子的掺杂引起了原硅团簇结构的重构；随着掺杂体系尺寸增大，2个钒原子（形成V-V键）逐渐被硅笼包裹。其次，以此结构为基础，通过分析平均键能、二阶能量差分和HOMO-LUMO能隙，研究了体系的稳定性。结果表明，V2Si12-/0团簇在各自体系中具有相对高的稳定性。此外，磁性分析发现，闭壳层V₂Si_n (n=8~17)体系的总自旋磁矩均为零，开壳层V2Sin- (n=8~17)体系分别拥有1 μB的总磁矩。分析极化率发现，V2Si8-/0拥有最大的平均极化率，具有强的非线性光学效应。拟合得到的光电子能谱、红外和拉曼光谱为进一步的实验研究提供了理论支持。热力学特性分析表明，研究体系在热力学上是稳定的。随着温度升高，定容热容和标准熵逐渐增大；随着压强增大，标准熵逐渐减小。

The study of silicon clusters has led to significant interest in transition metal atoms doped silicon clusters. In order to provide robust guidelines for future experimental and theoretical investigations of vanadium doped silicon nanomatrials, the geometric structures, stabilities and properties of V2Sin-/0 (n=8~17) clusters were systemically studied using density functional theory. Firstly, the lowest and lower lying energy structures of V2Sin-/0(n=8~17) clusters were globally predicted using the CALYPSO (crystal structure analysis by particle swarm optimization) searching method via the particle swarm optimization algorithm. Geometry optimization at the B3LYP/6-311+G(d) level revealed that two vanadium atoms tend to form V₂ bonds encapsulated gradually into silicon cages with an increasing number of silicon atoms. Secondly, based on the lowest energy structures, calculations of the average binding energy, second order energy difference, and HOMO-LUMO gaps indicated that the V2Si12-/0 clusters exhibit higher stability, respectively. In addition, magnetic properties analyses revealed that the total magnetic moment is zero for the closed-shell structures of V₂Si_n (n=8~17) clusters; However, the open-shell structures of V₂Si_n (n=8~17) clusters have magnetic moments with values of 1 μB. Upon polarizability analysis, V2Si8-/0 clusters with the highest mean dipole polarizability possess stronger nonlinear optical properties. Furthermore, the simulated PES(photoelectron spectroscopy), IR (infrared), and Raman spectra can provide theoretical guidance for future experimental investigations. Finally, the lowest energy structures of V₂Si_n (n=8~17) clusters are stable thermodynamically. Moreover, the heat capacity at constant volume (C_v) increases with the increasing of temperature, and standard entropy (S) decreases with temperature increasing.

国家自然科学基金资助项目(11904328，12104416)；郑州师范学院青年骨干教师培养计划(QNGG-211361)；郑州师范学院本科教学改革研究项目(JXGG-20773)；郑州师范学院优秀基层教学组织建设项目（物理与电子工程学院物理学教研室）资助。