高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (9): 1976-1984.doi: 10.7503/cjcu20180218

• 物理化学 • 上一篇    下一篇

硅基稀土掺杂团簇MSiq7(M=Eu, Sm, Yb; q=0, -1)结构预测与光电子能谱研究

蒋贤明, 王怀谦(), 曹宇, 孙之惠, 曹玉芳, 吴伟宾   

  1. 华侨大学工学院, 泉州 362021
  • 收稿日期:2018-03-19 出版日期:2018-07-30 发布日期:2018-07-30
  • 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:
    福建省自然科学基金(批准号: 2017J01001)、 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)和国家级大学生创新创业训练计划项目(批准号: 201710385024)资助.

Structure Prediction and Photoelectron Spectroscopy Study of Rare Earth-doped Silicon-based Clusters of MSiq7(M=Eu, Sm, Yb; q=0, -1)

JIANG Xianming, WANG Huaiqian*(), CAO Yu, SUN Zhihui, CAO Yufang, WU Weibin   

  1. College of Engineering, Huaqiao University, Quanzhou 362021, China
  • Received:2018-03-19 Online:2018-07-30 Published:2018-07-30
  • Contact: WANG Huaiqian E-mail:hqwang@hqu.edu.cn
  • Supported by:
    † Supported by the Natural Science Foundation of Fujian Province of China(No.2017J01001), the New Century Excellent Talents in Fujian Province University, China(No.2014FJ-NCET-ZR07), the Excellent Youth Talents in Fujian Province University, China(No.JA13009) and the National Undergraduate Training Programs for Innovation and Entrepreneurship, China(No.201710385024)

摘要:

采用随机踢球模型结合密度泛函理论, 在PBEPBE/RE/SDD/Si/6-311+G(d)水平下研究了中性和阴性的硅基稀土掺杂团簇MSiq7(M=Eu, Sm, Yb; q=0, -1)的几何结构、 稳定性及电子和磁学性质. 计算结果表明, 阴性团簇的基态结构是在五角双锥的双锥侧面外法向方向加入一个Si原子而形成的3D结构, 并且稀土原子M处于五角双锥的顶点; 中性团簇的最低能结构是一个畸变的双帽八面体, 并且M原子处于八面体的赤道面上. SmSi7-团簇在这3种稀土掺杂的团簇中具有最高的平均结合能和掺杂能, 是这3种稀土掺杂团簇中最稳定的一种. Si7团簇是非磁性团簇, 但是当M原子(M=Eu, Sm, Yb) 掺入其中时, 由于镧系元素独特的原子磁性, 使其变成了磁性团簇. 此外, 还模拟了各团簇前几种低能异构体的光电子能谱.

关键词: 原子团簇, 密度泛函理论, 结构优化, 磁性

Abstract:

The geometrical structures, relative stabilities, electronic properties and magnetism of anionic and neutral lanthanide metal-doped silicon clusters were systematically investigated by using the Saunders Kick global stochastic search technique combined with density functional theory(DFT) calculations at the PBEPBE/RE/SDD/Si/6-311+G(d) level of theory. The calculation results show that the ground state structure for anionic cluster is a 3D structure with the RE atom M sitting on top(or bottom) of the pentagonal bipyramid while adding another Si to the normal direction of it. The lowest energy structure of the neutral cluster is formed by substituting a Si atom on the equatorial surface of a distorted bicapped octahedral with an M atom. The SmSi7- cluster has the highest binding energy and doping energy in the three rare earth doped clusters, indicating that SmSi7- is the most stable cluster among them. When M atoms(M=Eu, Sm, Yb) were added into the Si7 cluster, due to their unique atomic magnetism, the non-magnetic Si7 cluster would be magnetized. In addition, the simulated photoelectron spectra(PES) of top-several isomers of each cluster were also presented, which could provide a theoretical basis for further experiments.

Key words: Atomic cluster, Density functional theory, Structural optimization, Magnetic property

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