双二十面体Agn(n=19, 23, 24, 25)团簇低能稳态构型的TS搜索
收稿日期: 2013-05-02
网络出版日期: 2013-06-27
基金资助
项目受国家自然科学基金(No. 51071065)和高等学校博士学科点专项科研基金(No. 20100161110001)资助.
A TS Search for Stable Configurations of Double Icosahedral Agn (n=19, 23, 24, 25) Clusters Linked by Sharing Atoms
Received date: 2013-05-02
Online published: 2013-06-27
Supported by
Project supported by the National Natural Science Foundation of China (Grant No. 51071065) and the Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20100161110001).
采用基于NEB的MEP的LST/QST方法, 发展了一种不依赖团簇初始结构而得到其低能稳态构型的过渡态搜索方法, 预测和分析了孤立与铰链双二十面体Agn (n=13, 19, 23, 24, 25)的低能稳态构型. 证实Ag13-Ih的低能稳态构型是一个含有五角双锥碎片的Ag13-C2扁平层状结构, 而Ag19-D5h的低能稳态构型则是在13原子二十面体上添加6原子组成Ag19-C1球形结构. 并且揭示Ag23-D3h, Ag24-D2h, Ag25-D5d与Agn (n=17～22)团簇一样, 其低能稳态构型也含有一个13原子的变形二十面体核心.
蒋元祺 , 彭平 , 文大东 , 韩绍昌 . 双二十面体Agn(n=19, 23, 24, 25)团簇低能稳态构型的TS搜索[J]. 化学学报, 2013 , 71(10) : 1429 -1434 . DOI: 10.6023/A13050470
A DMol3 molecular orbital package based on DFT theory is adopted to calculate the energetics and electronic structures of icosahedral Ag13 and double icosahedral Agn (n=19, 23, 24, 25) clusters. Ab initio MD simulation for Ag13 cluster at 300 K is also carried out in the micro-canonical ensemble (NVE). During optimization and total energy calculation, electronic exchange-correlation energy functions represented in reciprocal space with the PBE type under GGA approximation are used. A double-numerical basis set together with d-polarization functions (DNP) is chosen to describe the electronic wave functions of Ag atoms. And only core electrons described by the DFT Semi-core Pseudopots (DSPP) are calculated. All atomic positions in Agn (n=13, 19, 23, 24, 25) clusters are relaxed by geometry optimization under RMS force of 0.002 Ha/Å and RMS displacement of 0.005 Å. The calculation of total energy and electronic structure is followed by the geometry optimization with self-consistent field (SCF) tolerance of 1×10-5 Ha. Further, using linear synchronous transit (LST) and quadratic synchronous transit (QST) methods based on the minimum energy path (MEP) with the aid of the climbing image nudged elastic band (NEB) method, a new transition state (TS) search technique for stable configurations of clusters is developed, in which the stable configuration is independent on selected initial configurations. As this technique being applied to search the stable configurations of Agn (n=7, 13, 19, 23, 25) clusters, it is confirmed the low energy stable configuration of the isolated icosahedron Ag13-Ih is indeed a plate-shape layered structure Ag13-C2 including a pentagonal bipyramid segment. The ground state of the double icosahedra linked with intercross sharing atoms Ag19-D5h is also demonstrated to be a spherical geometry Ag19-C1 consisting of 6 atoms around a deformed Ag13 icosahedron. And similarly to Agn (n=17～22) clusters, all stable configurations of Ag23-D3h, Ag24-D2h, Ag25-D5d clusters have a deformed Ag13 icosahedral nucleus as reported in literatures.
Key words： Agn cluster; stable configuration; TS search; DMol3
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