SnnSm(n=1~9)团簇结构稳定性与磁学性质的理论研究

doi:10.7503/cjcu20160318

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (10): 1840.doi: 10.7503/cjcu20160318

Sn_nSm(n=1~9)团簇结构稳定性与磁学性质的理论研究

孙林¹, 王怀谦^1,²(), 吴梦³, 李慧芳¹, 李孝义¹, 杜丹¹, 沙蕊¹

1. 华侨大学工学院, 泉州 362021
2. 北京计算科学研究中心, 北京 100094
3. 北京北汽模塑科技有限公司, 北京 102606

收稿日期:2016-05-09 出版日期:2016-10-10 发布日期:2016-09-20
作者简介:联系人简介: 王怀谦, 男, 博士, 副教授, 主要从事纳米团簇与光电子能谱研究. E-mail:hqwang@hqu.edu.cn
基金资助:
福建省高校新世纪优秀人才支持计划项目(批准号: 2014FJ-NCET-ZR07)、福建省高校杰出青年科研人才培育计划项目(批准号: JA13009)和福建省自然科学基金(批准号: 2014J05006)资助

Theoretical Studies on the Structure Stability and Magnetic Properties of Sn_nSm(n=1—9) Clusters^†

SUN Lin¹, WANG Huaiqian^1,^2,^*(), WU Meng³, LI Huifang¹, LI Xiaoyi¹, DU Dan¹, SHA Rui¹

1. College of Engineering, Huaqiao University, Quanzhou 362021, China
2. Beijing Computational Science Research Center, Beijing 100094, China
3. Beijing Beiqi Mould & Plastic Technology Co. Ltd., Beijing 102606, China

Received:2016-05-09 Online:2016-10-10 Published:2016-09-20
Contact: WANG Huaiqian E-mail:hqwang@hqu.edu.cn
Supported by:
† Supported by the Program for New Century Excellent Talents in Fujian Province University, China(No.2014FJ-NCET-ZR07), the Program for Excellent Youth Talents in Fujian Province University, China(No.JA13009) and the Natural Science Foundation of Fujian Province, China(No.2014J05006)

摘要/Abstract

摘要：

采用Saunders全局优化随机踢球模型与密度泛函理论相结合的方法, 在B3LYP/SDD理论水平下研究了锡基原子团簇Sn_n(n=2~10)及锡基稀土原子钐掺杂团簇Sn_nSm(n=1~9)的几何结构、稳定性、电子性质和磁性. 结果表明, 团簇Sn_nSm(n=1~9)中掺杂的钐原子通常位于主团簇的表面, 掺杂团簇的基态结构更倾向于具有较高对称性的三维结构; 二元锡基混合团簇的平均结合能变大, 稳定性增强, 这主要归因于Sn—Sm键比Sn—Sn键的键能大, 具有更强的相互作用; 掺杂团簇具有较高的磁性, 其总磁矩主要源自于钐原子4f电子的贡献; 随着团簇尺寸的增加, 二元团簇的总磁矩呈现出趋于饱和的现象.

关键词: 原子团簇, 密度泛函理论, 磁矩, 踢球模型

Abstract:

The geometrical structures, relative stabilities, electronic properties and magnetism of tin clusters and bimetallic complexes of tin clusters with one samarium atom Sn_nSm(n=1—9) were investigated with the Saunders “Kick” global stochastic search technique combined with density functional theory(DFT) calculations at the B3LYP/SDD level of theory. The results are as follows: (1) Samarium atom usually located on the surface in the doped tin-based with one samarium atom clusters. And the ground-state structures of the Sn_nSm(n=1—9) clusters prefer to three-dimensional structure with higher symmetry; (2) after doping samarium atom in the Sn-based cluster, the cluster has the increase average binding energy which should owe to the fact that the bonding energy of Sn—Sm bond is higher than Sn—Sn bond and has the stronger interaction; (3) the doped Sn-based with one samarium atom cluster has large magnetic moments, and the contribution of magnetic moment almost comes from 4f electron orbit of the samarium atom, while the contribution of tin atoms is negligible. With the increase of cluster’s size, bimetallic complexes cluster has the special phenomenon that the total magnetic moment tends to be stable.

Key words: Atomic cluster, Density functional theory, Magnetic moment, Kick model

中图分类号:

O641

TrendMD:

孙林, 王怀谦, 吴梦, 李慧芳, 李孝义, 杜丹, 沙蕊. Sn_nSm(n=1~9)团簇结构稳定性与磁学性质的理论研究. 高等学校化学学报, 2016, 37(10): 1840.

SUN Lin, WANG Huaiqian, WU Meng, LI Huifang, LI Xiaoyi, DU Dan, SHA Rui. Theoretical Studies on the Structure Stability and Magnetic Properties of Sn_nSm(n=1—9) Clusters^†. Chem. J. Chinese Universities, 2016, 37(10): 1840.

图/表 9

Fig.1 Structure, symmetry point group and electronic state of the Snn(n=2—10) cluster, using B3LYP/SDD calculations

Table 1 Average binding energies of the Snn(n=2—10)

Structure	E_b/eV			Structure	E_b/eV
Structure	B3LYP/SDD		CCSD(T)/cc-pVTZ-PP	Expt.^[30]	B3LYP/SDD	CCSD(T)/cc-pVTZ-PP	Expt.^[30]
Sn₂	0.88	1.07	0.94	Sn₇	2.09	2.48	2.37
Sn₃	1.41	1.50	1.65	Sn₈	2.04
Sn₄	1.80	1.98	1.94	Sn₉	2.08
Sn₅	1.88	2.15	2.11	Sn₁₀	2.15
Sn₆	1.99	2.34	2.28

Fig.2 Structure, symmetry point group, electronic state and relative energy(eV) of the lower-lying isomers SnnSm(n=1—9) cluster

Fig.3 Average binding energy for the ground-state structures of SnnSm(a) and Snn+1(b) clusters and ΔEb(c)

Fig.4 Second order difference energy of SnnSm(a) and Snn+1(b) clusters

Fig.5 HOMO-LUMO energy gap of the ground-state structures of SnnSm clusters

Fig.6 Total magnetic moments of SnnSm clusters

Fig.7 Magnetic moments contribution of 6s,4f and 5d states for Sm atom in SnnSm clusters and local magnetic moments of the Sn and Sm atom

Table 2 Valence electron configuration of Sm atom in the SnnSm(n=1—9) cluster

Structure	Valence electron configuration
SnSm	6s^1.204f^6.005d^0.186p^0.06
Sn₂Sm	5p^0.036s^0.714f^5.985d^0.466p^0.03
Sn₃Sm	6s^0.664f^5.995d^0.406p^0.06
Sn₄Sm	6s^0.434f^5.995d^0.586p^0.09
Sn₅Sm	6s^0.494f^5.995d^0.576p^0.087p^0.02
Sn₆Sm	6s^0.354f^5.995d^0.806p^0.146d^0.017p^0.03
Sn₇Sm	4f^5.995d^0.716p^0.037s^0.287p^0.08
Sn₈Sm	6s^0.384f^5.995d^0.776p^0.166d^0.017p^0.13
Sn₉Sm	4f^5.985d^0.766p^0.056d^0.017p^0.048s^0.29

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Sn_nSm(n=1~9)团簇结构稳定性与磁学性质的理论研究

Theoretical Studies on the Structure Stability and Magnetic Properties of Sn_nSm(n=1—9) Clusters^†

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SnnSm(n=1~9)团簇结构稳定性与磁学性质的理论研究

Theoretical Studies on the Structure Stability and Magnetic Properties of SnnSm(n=1—9) Clusters†

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Sn_nSm(n=1~9)团簇结构稳定性与磁学性质的理论研究

Theoretical Studies on the Structure Stability and Magnetic Properties of Sn_nSm(n=1—9) Clusters^†