PtnAl (n=18)小团簇的密度泛函理论研究

温俊青; 夏涛; 王俊斐

doi:10.7498/aps.63.023103

摘要

采用密度泛函理论方法，在BPW91/LANL2DZ水平下详细研究了PtnAl（n=18）团簇的几何结构、稳定性和电子性质. 同时，分析了团簇的结构演化规律、平均结合能、二阶能量差分、能隙、磁性、Mulliken电荷和电极化率. 结果表明：除Pt2Al外，所有PtnAl（n=18）团簇的基态几何结构都可以用Al原子替换Ptn+1基态构型中的Pt原子得到，且Al原子位于较高的配位点上. 二阶能量差分、能隙的分析结果表明，PtAl和Pt4Al团簇相对其他团簇具有较高的稳定性. Mulliken电荷分析表明，Al原子所带的电荷转移到Pt原子上，Al原子是电荷的捐赠者. 磁性的分析说明，单个Al原子的加入对Ptn团簇的平均每原子磁矩随尺寸的变化趋势没有影响，但总体上降低了Ptn团簇的平均磁矩. 极化率的研究表明，富Pt团簇的非线形光学效应强，容易被外场极化.

关键词:

Abstract

The geometries, stabilities and electronic properties of PtnAl (n=18) clusters are calculated using density functional theory at BPW91/LANL2DZ level. The stabilities of the ground states of PtnAl (n=18) clusters are discussed by means of the binding energy, the second difference in energy and energy gaps, and the magnetic properties. Mulliken charges are studied. The growth patterns for different sized PtnAl (n=18) clusters are of Al-substituted Ptn+1 clusters and they keep a similar framework of the most stable Ptn+1 clusters except Pt2Al. Al atoms in the ground state PtnAl isomer tend to occupy the most highly coordinated positions. The analyses of stabilities show that PtAl and Pt4Al are more stable than other clusters. Mulliken population analysis shows that charges are transferred from Al atoms to Pt atoms, which indicates that Al atom acts as electron donor in all PtnAl clusters. The analysis of magnetic property shows that doping an Al atom reduces the average atomic magnetic moment of the host Pd cluster. Pt-rich clusters which have a strong nonlinear optical effect and are easy to polarize by external electromagnetic field.

Keywords:

作者及机构信息

1.
西安石油大学理学院, 西安 710065;

2.
西北大学现代物理研究所, 西安 710069

基金项目: 国家自然科学基金（批准号：11247229）、陕西省教育厅科研计划项目（批准号：2013JK0629）和省级大学生创新创业训练计划项目（批准号：Z12187）资助的课题.

Authors and contacts

1.
College of Science, Xi’an Shiyou University, Xi’an 710065, China;

2.
Institute of Modern Physics, Northwest University, Xi’an 710069, China

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 11247229), Science Research Program Funded by Shaanxi Provincial Education Department, China (Grant No. 2013JK0629) and Provincial College Students Innovation and Entrepreneurship Training Program, China (Grant No. Z12187).

参考文献

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施引文献

[1]	Sebetci A, Gvenc Z B 2003 Surf. Sci. 525 66
[2]	Xiao L, Wang L C 2004 J. Phys. Chem. A 108 8605
[3]	Tian W Q, Ge M, Sahu B R, Wang D X, Yamada T, Mashiko S 2004 J. Phys. Chem. A 108 3806
[4]	Futschek T, Hafner J, Marsman M 2006 J. Phys.: Condens. Matter 18 9703
[5]	Zhang X R, Yang X, Ding X L 2012 Chin. Phys. B 21 093601 (in Chinese) [张秀荣, 杨星, 丁迅雷 2012 中国物理B 21 093601]
[6]	Cheng D J, Wang W C, Huang S P 2006 J. Phys. Chem. B 110 16193
[7]	Corina M, Claude D, Daniel D 2002 J. Catal. 212 125
[8]	Yuan D W, Wang Y, Zeng Z 2005 J. Phys. 122 114
[9]	Gou J J, Yang J X, Dong D 2006 J. Mol. Struct. (Theochem) 764 117
[10]	Guo J J, Yang J X, Xu S L 2008 J. At. Mol. Phys. 25 838 (in Chinese) [郭建军, 杨继先, 许生林2008 原子与分子 25 838]
[11]	Zhang X R, Hong L L, Cui Y N, Zhang W 2009 J. Mol. Sci. 25 192 (in Chinese) [张秀荣, 洪伶俐, 崔彦娜, 张伟 2009 分子科学学报 25 192]
[12]	Mandal M, Kundu S, Sau T K 2003 Chem. Mater. 15 3710
[13]	Xu Y, Ruban A V, Mavrikakis M 2004 J. Am. Chem. Soc. 126 4717
[14]	Baletto F, Ferrando R, Fortunelli A 2002 J. Chem. Phys. 16 3856
[15]	Jacob T, Muller R P, Goddard W A 2003 J. Phys. Chem. B 107 9465
[16]	Wakabayashi N, Takeichi M, Uchida H 2005 J. Phys.Chem. B 109 5836
[17]	Yamagishi S, Fujimoto T, Inada Y 2005 J. Phys. Chem. B 109 8899
[18]	Chen Y Y, Shi Z, Zhou S M, Rui W B, Du J 2013 Chin. Phys. B 22 067504
[19]	Liu G, Wang W, Niu Y, Wu W 2001 Corros. Sci. Prot. Technol. 13 106 (in Chinese) [刘刚, 王文, 牛焱, 吴维 2001 腐蚀科学与防护技术 13 106]
[20]	Pang Y, Guan H R, Sun X F, Jiang X X 1997 Corros. Sci. Prot. Technol. 9 34 (in Chinese) [庞英, 管恒荣, 孙晓峰, 姜晓霞 1997 腐蚀科学与防护技术 9 34]
[21]	Zhang J J, Zhang H 2010 Acta Phys. Sin. 59 4143 (in Chinese) [张建军, 张红 2010 59 4143]
[22]	Michael W, Frank K, Tapan C 2008 J. Alloys Compd. 455 130
[23]	Niu W X, Zhang H, Gong M, Cheng X L 2013 Chin. Phys. B 22 066802
[24]	Huang Y, Gou H Y, Liao Z W, Sun Q Q, Zhang W, Ding S J 2010 Acta Phys. Sin. 59 2057 (in Chinese) [黄玥, 苟鸿雁, 廖忠伟, 孙清清, 张卫, 丁士进 2010 59 2057]
[25]	L J, Qin J P, Wu H S 2013 Acta Phys. Sin. 63 053101 (in Chinese) [吕瑾, 秦键萍, 武海顺 2013 63 053101]
[26]	Wen J Q, Jiang Z Y, Li J Q, Cao L K, Chu S Y 2010 Int. J. Quan. Chem. 110 1368
[27]	Wen J Q, Jiang Z Y, Hou Y Q, Li J Q, Chu S Y 2010 J. Mol. Struct. (Theochem) 949 91
[28]	Zhao G F, Zhang J, Jing Q 2007 J. Chem. Phys. 127 234312
[29]	Xiang J, Wei S H, Yan X H, You J Q, Mao Y L 2004 J. Chem. Phys. 120 4251
[30]	Guo L 2009 Comp. Mater. Sci. 45 951
[31]	Zhang X R, Gao C H, Wu L Q, Tang H S 2010 Acta Phys. Sin. 59 5249 (in Chinese) [张秀荣, 高从花, 吴礼清, 唐会帅 2010 59 5429]

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