Ca<sub>2</sub>Si<sub>n</sub>(n=1~9)团簇结构、稳定性与光谱性质的理论研究

张帅; 张颖颖; 张萍; 李根全; 吕林霞; 卢成

doi:doi:10.3788/aos201333.1116003

光学学报, 2013, 33 (11): 1116003, 网络出版: 2013-09-17

Ca₂Si_n(n=1~9)团簇结构、稳定性与光谱性质的理论研究

Theoretical Study of the Structural, Stability and Spectral Properties of Ca₂Si_n(n=1~9) Clusters

论文大纲

张帅 ^*张颖颖张萍李根全吕林霞卢成

作者单位

南阳师范学院物理与电子工程学院, 河南南阳 473061

光谱学 Ca2Sin(n=1~9)团簇结构与稳定性密度泛函理论 spectroscopy Ca2Sin cluster (n=1~9) structure and stability density functional theory

摘要

采用密度泛函理论(DFT)中的杂化密度泛函B3LYP方法，在6-311G (d)基组的水平上研究了Ca2Sin(n=1~9)团簇的平衡几何结构、稳定性与光谱性质。结构优化表明：Ca2Sin团簇的基态绝大多数为立体结构（除了n=1，2）。在获得的最低能量结构基础上计算并分析了掺杂团簇的平均结合能、二阶能量差分、分裂能、能隙与光谱性质与团簇尺寸的变化关系，计算结果发现：Ca原子的掺入使得体系的化学稳定性降低，Ca2Si5，Ca2Si7与Ca2Si9是幻数结构。从光谱性质分析来看，Ca2Si5团簇与Ca2Si9团簇的红外较强吸收峰的个数较多，而Ca2Si7团簇的红外较强吸收峰的个数则较少；Ca2Si5团簇的拉曼只有一个较强峰值且位于低频段内，Ca2Si7团簇与Ca2Si9团簇的拉曼较强峰的个数较多。

Abstract

The geometries, stabilities, and spectral properties of Ca2Sin(n=1~9) clusters are systematically investigated by using first principles calculations based on the hybrid density functional theory at the B3LYP / 6-311G (d) level. The optimized geometries indicate that the most stable structures of Ca2Sin clusters are three-dimensional structures for n=3~9. On the basis of the obtained lowest-energy geometries, the size dependence of cluster properties, such as averaged binding energies, second-order energy differences, fragmentation energies, HOMO-LUMO gaps and spectral properties, are discussed. The calculated results show that the impurity Ca atoms in the Ca2Sin clusters enhance the chemical stability of the silicon framework. The magic clusters are found at n=5, 7 and 9. In addition, the spectral analysis indicates, the number of the infrared (IR) absorption peaks of Ca2Si5 and Ca2Si9 is more, but Ca2Si7 is less. The Raman absorption peak of Ca2Si5 is only one and appears in the low frequency band, on the contray, Ca2Si7 and Ca2Si9 have more Raman absorption peaks.

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张帅, 张颖颖, 张萍, 李根全, 吕林霞, 卢成. Ca₂Si_n(n=1~9)团簇结构、稳定性与光谱性质的理论研究[J]. 光学学报, 2013, 33(11): 1116003. Zhang Shuai, Zhang Yingying, Zhang Ping, Li Genquan, Lü Linxia, Lu Cheng. Theoretical Study of the Structural, Stability and Spectral Properties of Ca₂Si_n(n=1~9) Clusters[J]. Acta Optica Sinica, 2013, 33(11): 1116003.

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