Cun-1Au (n=2&#8211;10)团簇结构、静态极化率及吸收光谱的第一性原理研究

钱帅; 郭新立; 王家佳; 余新泉; 吴三械; 于金

doi:10.7498/aps.62.057803

摘要

采用遗传算法, 得到贵金属混合团簇Cun-1Au (n=2–10)的稳态结构, 并采用分别基于静态及含时的密度泛函理论的第一性原理方法计算了团簇的静态极化率和吸收光谱. 由于d电子屏蔽效应的增强, 金原子的引入会导致团簇静态极化率的降低, 但立体的构型能减小这种影响. 基于含时密度泛函理论的第一性原理计算得到的吸收光谱指出, 这种屏蔽效应同时导致共振强度的明显下降. d轨道对跃迁贡献的进一步计算, 指出d轨道成分是团簇的光激发中的主要贡献者, 但d电子的屏蔽作用并不会直接导致在激发中d轨道贡献的提升. 针对固定尺寸体系, Cu6-nAun (n=0–6) 团簇的研究进一步论证了此观点. 计算的光谱与实验值能很好地对应, 并且比其他更早的理论计算更为接近实验值.

关键词:

Abstract

The structures of Cun-1Au clusters are examined using the genetic algorithm, and the static polarizabilities and optical absorption spectra are investigated by first principles computations within the static and time-dependent versions of the density functional theory. The static polarizabilities decrease after being doped by one Au atom due to the strengthened screening effect of d electrons, which can also be weakened by three-dimensional structures. The optical spectra computed within the time-dependent density functional theory indicate that the screening effect also leads to the quenching of oscillator strengths. A deeper analysis of d-orbit indicates d-orbit is the main contributor in the optical excitation while its growing up is not directly influenced by the strengthened screening effect. The research on Cu6-nAun (n=0–6) clusters in a fixed size system verifies our arguments further. Our calculation results are in good agreement with the experimental data on the optical absorption spectra, which are closer to the experimental data than the earlier theoretical results.

Keywords:

作者及机构信息

1.
东南大学材料科学与工程学院, 南京 211189;

2.
东南大学江苏省先进金属材料高技术研究重点实验室, 南京 211189;

3.
南京大学化学化工学院, 南京 210093

基金项目: 国家自然科学基金(批准号: 21173041) 资助的课题.

Authors and contacts

1.
School of Materials Science and Engineering, Southeast University, Nanjing 211189, China;

2.
Jiangsu Key Laboratory of Advanced Metallic Materials, Southeast University, Nanjing 211189, China;

3.
School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 21173041).

参考文献

[1]	Cho E C, Pedro H C, Xia Y N 2009 Adv. Mater. 21 1
[2]	Ming T, Feng W, Tang Q 2009 Am. Chem. Soc. 131 16350
[3]	Kumar P S, Santos I P, Gonzalezi B R 2008 Nanotechnology 19 015606
[4]	Li X Y, Zhang Y, Jiao L S 2006 Acta Phys. Sin 55 2078 (in Chinese) [李向阳, 张芸, 焦力实 2006 55 2078]
[5]	Ren X F, Zhan C L, Huang Y F 2008 Chin. Phys. Lett. 25 559
[6]	Yang H, Yang L D, Ma Y 2005 Chin. Phys. 14 1665
[7]	Gao H J, Liu F, Chen S T 2005 Chin. Phys. 14 2269
[8]	Xu Z C, Gao H J, Xiao C W 2008 Chin. Phys. B 17 2066
[9]	Idrobo J C, Walkosz W, Yip S F, Oeguet S, Wang J L, Jellinek J 2007 Phys. Rev. B 76 20542220
[10]	Baishya K, Idrobo J C, Ogut S 2011 Phys. Rev. B 83 24540224
[11]	Lecoultre S 2011 J. Chem. Phys. 134 74302
[12]	Lecoultre S, Rydlo A, Felix C 2011 J. Chem. Phys. 134 0743037
[13]	Wang H Q, Kuang X Y, Li H F 2010 Phys. Chem. Chem. Phys. 12 5156
[14]	Wang J, Wang G, Zhao J 2002 Phys. Rev. B 66 35418
[15]	Beeke A D 1993 J. Chem. Phys. 98 5648
[16]	Lee C, Yang W, Parr R G 1988 Phys. Rev. B 37 785
[17]	Mielich B, Savin A, Stoll H, Preuss H 1989 Chem. Phys. Lett. 157 200
[18]	Wang H Y, Li X B, Tang Y J, King R B, Schaefer H F 2007 Chin. Phys. 16 1660
[19]	Zhao Y, Li Z, Yang J 2009 Phys. Chem. Chem. Phys. 11 2329
[20]	Tanaka H, Neukermans S, Janssens E, Silverans R E, Lievens P 2003 J. Chem. Phys. 119 7115
[21]	Hay P J, Wadt W R 1985 J. Chem. Phys. 82 270
[22]	Bishea G A, Pinegar J C, Morse M D 1991 J. Chem. Phys. 95 5630
[23]	Oganov A R 2010 Modern Methods of Crystal Structure Prediction (Wiley-VCH)
[24]	Nagle J K 1990 J. Am. Chem. Soc. 112 4741
[25]	Calaminici, Patrizia 2000 J. Chem. Phys. 113 2199
[26]	Ogut S, Idrobo J C, Jellinek J 2006 Journal of Cluster Science 17 609
[27]	Vitto Del A, Sousa C, Illas F, Pacchioni G 2004 J. Chem. Phys. 121 7457
[28]	Bosko S I, Moskaleva L V, Matveev A V, Rosch N 2007 J. Chem. Phys. 111 6870
[29]	Wang X, Wan X, Zhou H 2002 J. Mol. Struct.: Theochem 579 221
[30]	Shenstone A G 1948 Philos. Trans. R. Soc. London A 241 297
[31]	Lecoultre S, Rydlo A, Felix C 2011 Journal of Chemical Physics 134 0743037
[32]	Bishea G A 1991 J. Chem. Phys. 95 5630
[33]	Bishea G A 1991 J. Chem. Phys. 95 8765
[34]	Vasiliev I, Ogut S, Chelikowsky J R 1997 Phys. Rev. Lett. 78 4805
[35]	Jackson K A, Yang M, Chaudhuri I 2005 Phys. Rev. A 71 033205

施引文献

[1]	Cho E C, Pedro H C, Xia Y N 2009 Adv. Mater. 21 1
[2]	Ming T, Feng W, Tang Q 2009 Am. Chem. Soc. 131 16350
[3]	Kumar P S, Santos I P, Gonzalezi B R 2008 Nanotechnology 19 015606
[4]	Li X Y, Zhang Y, Jiao L S 2006 Acta Phys. Sin 55 2078 (in Chinese) [李向阳, 张芸, 焦力实 2006 55 2078]
[5]	Ren X F, Zhan C L, Huang Y F 2008 Chin. Phys. Lett. 25 559
[6]	Yang H, Yang L D, Ma Y 2005 Chin. Phys. 14 1665
[7]	Gao H J, Liu F, Chen S T 2005 Chin. Phys. 14 2269
[8]	Xu Z C, Gao H J, Xiao C W 2008 Chin. Phys. B 17 2066
[9]	Idrobo J C, Walkosz W, Yip S F, Oeguet S, Wang J L, Jellinek J 2007 Phys. Rev. B 76 20542220
[10]	Baishya K, Idrobo J C, Ogut S 2011 Phys. Rev. B 83 24540224
[11]	Lecoultre S 2011 J. Chem. Phys. 134 74302
[12]	Lecoultre S, Rydlo A, Felix C 2011 J. Chem. Phys. 134 0743037
[13]	Wang H Q, Kuang X Y, Li H F 2010 Phys. Chem. Chem. Phys. 12 5156
[14]	Wang J, Wang G, Zhao J 2002 Phys. Rev. B 66 35418
[15]	Beeke A D 1993 J. Chem. Phys. 98 5648
[16]	Lee C, Yang W, Parr R G 1988 Phys. Rev. B 37 785
[17]	Mielich B, Savin A, Stoll H, Preuss H 1989 Chem. Phys. Lett. 157 200
[18]	Wang H Y, Li X B, Tang Y J, King R B, Schaefer H F 2007 Chin. Phys. 16 1660
[19]	Zhao Y, Li Z, Yang J 2009 Phys. Chem. Chem. Phys. 11 2329
[20]	Tanaka H, Neukermans S, Janssens E, Silverans R E, Lievens P 2003 J. Chem. Phys. 119 7115
[21]	Hay P J, Wadt W R 1985 J. Chem. Phys. 82 270
[22]	Bishea G A, Pinegar J C, Morse M D 1991 J. Chem. Phys. 95 5630
[23]	Oganov A R 2010 Modern Methods of Crystal Structure Prediction (Wiley-VCH)
[24]	Nagle J K 1990 J. Am. Chem. Soc. 112 4741
[25]	Calaminici, Patrizia 2000 J. Chem. Phys. 113 2199
[26]	Ogut S, Idrobo J C, Jellinek J 2006 Journal of Cluster Science 17 609
[27]	Vitto Del A, Sousa C, Illas F, Pacchioni G 2004 J. Chem. Phys. 121 7457
[28]	Bosko S I, Moskaleva L V, Matveev A V, Rosch N 2007 J. Chem. Phys. 111 6870
[29]	Wang X, Wan X, Zhou H 2002 J. Mol. Struct.: Theochem 579 221
[30]	Shenstone A G 1948 Philos. Trans. R. Soc. London A 241 297
[31]	Lecoultre S, Rydlo A, Felix C 2011 Journal of Chemical Physics 134 0743037
[32]	Bishea G A 1991 J. Chem. Phys. 95 5630
[33]	Bishea G A 1991 J. Chem. Phys. 95 8765
[34]	Vasiliev I, Ogut S, Chelikowsky J R 1997 Phys. Rev. Lett. 78 4805
[35]	Jackson K A, Yang M, Chaudhuri I 2005 Phys. Rev. A 71 033205

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Cun-1Au (n=2–10)团簇结构、静态极化率及吸收光谱的第一性原理研究

First principles study of structures, static polarizabilities and optical absorption spectra of Cun-1Au (n=2–10) clusters

摘要

Abstract

作者及机构信息

1.
东南大学材料科学与工程学院, 南京 211189;

2.
东南大学江苏省先进金属材料高技术研究重点实验室, 南京 211189;

3.
南京大学化学化工学院, 南京 210093

Authors and contacts

1.
School of Materials Science and Engineering, Southeast University, Nanjing 211189, China;

2.
Jiangsu Key Laboratory of Advanced Metallic Materials, Southeast University, Nanjing 211189, China;

3.
School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China

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Cun-1Au (n=2–10)团簇结构、静态极化率及吸收光谱的第一性原理研究

First principles study of structures, static polarizabilities and optical absorption spectra of Cun-1Au (n=2–10) clusters

摘要

Abstract

作者及机构信息

1. 东南大学材料科学与工程学院, 南京 211189; 2. 东南大学江苏省先进金属材料高技术研究重点实验室, 南京 211189; 3. 南京大学化学化工学院, 南京 210093

Authors and contacts

1. School of Materials Science and Engineering, Southeast University, Nanjing 211189, China; 2. Jiangsu Key Laboratory of Advanced Metallic Materials, Southeast University, Nanjing 211189, China; 3. School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China

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关于我们

1.
东南大学材料科学与工程学院, 南京 211189;

2.
东南大学江苏省先进金属材料高技术研究重点实验室, 南京 211189;

3.
南京大学化学化工学院, 南京 210093

1.
School of Materials Science and Engineering, Southeast University, Nanjing 211189, China;

2.
Jiangsu Key Laboratory of Advanced Metallic Materials, Southeast University, Nanjing 211189, China;

3.
School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China