物理化学学报 >> 2013, Vol. 29 >> Issue (07): 1433-1440.doi: 10.3866/PKU.WHXB201304272

理论与计算化学 上一篇    下一篇

TinO2和TinO2-(n=1-10)团簇的几何结构、电子和磁性质

聂静1, 卢章辉1, 姚军2, 桂田1, 陈祥树1   

  1. 1 江西师范大学化学化工学院, 江西省无机膜材料工程技术研究中心, 南昌 330022;
    2 中国人民解放军61135部队, 北京 100082
  • 收稿日期:2013-01-31 修回日期:2013-04-26 发布日期:2013-06-14
  • 通讯作者: 卢章辉, 陈祥树 E-mail:luzh@jxnu.edu.cn;cxs66cn@jxnu.edu.cn
  • 基金资助:

    国家高新技术研究发展计划(863)(2012AA03A609); 国家自然科学基金(21103074); 江西省教育厅科技项目(GJJ12190)及江西师范大学青年英才培育计划资助项目

Structural, Electronic and Magnetic Properties of TinO2 and TinO2- (n=1-10) Clusters

NIE Jing1, LU Zhang-Hui1, YAO Jun2, GUI Tian1, CHEN Xiang-Shu1   

  1. 1 Jiangxi Inorganic Membrane Materials Engineering Research Centre, College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022, P. R. China;
    2 Unit 61135 of General Staff Department, Beijing 100082, P. R. China
  • Received:2013-01-31 Revised:2013-04-26 Published:2013-06-14
  • Contact: LU Zhang-Hui, CHEN Xiang-Shu E-mail:luzh@jxnu.edu.cn;cxs66cn@jxnu.edu.cn
  • Supported by:

    The project was supported by the National High Technology Research and Development Program of China (863) (2012AA03A609), National Natural Science Foundation of China (21103074), Jiangxi Provincial Education Department, China (GJJ12190), and Sponsored Program for Cultivating Youths of Outstanding Ability in Jiangxi Normal University, China.

摘要:

基于密度泛函理论(DFT)的B3LYP方法, 研究了TinO2和TinO2- (n=1-10)团簇的几何结构、电子结构以及磁性. 结果表明, 两个氧以分离的原子状态吸附在金属团簇的表面, 呈现出以一个钛原子为中心的O-Ti-O 的相邻吸附形式. 中性团簇和阴离子团簇的能量最低结构相似. 稳定性分析表明TinO2具有很高的稳定性, 特别是TiO2和Ti7O2. 此外, 详细讨论了团簇的电离势、电子亲和能、电子解离能和能隙. 基于最低能量结构, 讨论了团簇的磁性, 发现电荷从Ti 原子向O原子转移, 并且电荷转移主要发生在TinO2的Ti-3d、Ti-4s和O-2p轨道. 磁性团簇中反铁磁序占据主导, 磁矩主要来源Ti-3d电子的贡献, 而两个氧原子的贡献非常小.

关键词: 密度泛函理论, 团簇, 稳定性, 磁性, 轨道杂化

Abstract:

The structural, electronic, and magnetic properties of TinO2 and TinO2- (n=1-10) clusters are studied using density functional theory with the B3LYP hybrid density functional. The calculated geometries show that the two dissociative oxygen atoms remain on the surface of pure Tin clusters and do not change the geometry of Tin much. The two oxygen atoms exist in the vicinity of TinO2 clusters, exhibiting an O-Ti-O connection in TinO2. The geometries of the lowest-energy neutral and anionic clusters are similar. Stability analyses reveal that TinO2 clusters are highly stable, especially TiO2 and Ti7O2 clusters. In addition, the ionization potentials, electron affinities, electron detachment energies, and energy gaps of the systems are carefully investigated. On the basis of their optimized structures, we discuss the magnetic properties of the two systems. Charge transfer occurs from Ti to O atoms, mainly between Ti-3d, Ti-4s, and O-2p orbitals of TinO2 clusters. Antiferromagnetic ordering is dominant in the two systems. The magnetic moment of TinO2 is clearly dominated by the localized 3d electrons of Ti atoms, and the two oxygen atoms contribute a very small amount of spin in TinO2 clusters.

Key words: Density functional theory, Cluster, Stability, Magnetism, Orbital hybridization

MSC2000: 

  • O641