Citation: CAO Fei, TAN Kai, LIN Meng-Hai. Geometric and Electronic Structures of Hexanuclear Binary Ta/Rh Mixed Clusters[J]. Acta Physico-Chimica Sinica, ;2010, 26(11): 3061-3066. doi: 10.3866/PKU.WHXB20101112 shu

Geometric and Electronic Structures of Hexanuclear Binary Ta/Rh Mixed Clusters

CAO Fei ^1,2, ,
TAN Kai ² ,
LIN Meng-Hai ²

1.
1. College of Chemistry and Chemical Engineering, Jiujiang University, Jiujiang 332005, Jiangxi Province, P. R. China;
2. Departmental of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian Province, P. R. China

Received Date: 13 June 2010
Available Online: 17 September 2010
Fund Project: 国家自然科学基金(20873107, 20373053)资助项目 (20873107, 20373053)

Density functional theory (DFT) was employed to investigate the geometric and electronic properties of a series of hexanuclear binary Ta/Rh clusters. The results show that most of the stable structures of the Ta/Rh mixed clusters have low symmetry and belong to the C₁ or C_s point groups while the [Ta₂Rh₄Cl₄H₈(CN)₆]^4- clusters are highly symmetric (C_2h or C_4v). The energy gaps (△E_H-L) between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the mixed clusters are narrow and within 0.52-1.00 eV. A frontier orbital analysis of the mixed clusters clearly shows that the molecular orbitals are mainly composed of the d-orbitals of the skeleton metal atoms. When more rhodium atoms are substituted for tantalum atoms, the Ta—Rh bond has a greater influence on the stable structures of the mixed clusters and the influence of Ta—Ta bond decreases while the Rh—Rh bond has a non-bonding or anti-bonding nature.
- Density functional theory,
- Transition-metal cluster,
- Metal bond,
- Tantalum,
- Rhodium
1. [1]
  
  1. Braunstein, P.; Oro, L. A.; Raithby, P. R. Metal clusters in chemistry. Weinheim: Wiley-VCH, 1999
2. [2]
  2. Yan, B. B.; Zhou, H. J.; Lachgar, A. Inorg. Chem., 2003, 42: 8818
3. [3]
  3. Zhou, H. J.; Day, C. S.; Lachgar, A. Chem. Mater., 2004, 16: 4870
4. [4]
  4. Yan, Z. H.; Day, C. S.; Lachgar, A. Inorg. Chem., 2005, 44: 4499
5. [5]
  5. Zhang, J. J.; Lachgar, A. J. Am.Chem. Soc., 2007, 129: 250
6. [6]
  6. Zhou, H. J.; Strates, K. C.; Muáoz, M. A.; Little, K. J.; Pajerowski, D. M.; Meisel, M. W.; Talham, D. R.; Lachgar, A. Chem. Mater., 2007, 19: 2238
7. [7]
  7. Zhou, H. J.; Lachgar, A. Crystal Growth&Design, 2006, 6: 2384
8. [8]
  8. Zhang, J. J.; Zhao, Y.; Gamboa, S. A.; Lachgar, A. Crystal Growth &Design, 2008, 8: 172
9. [9]
  9. Zhang, J. J.; Day, C. S.; Harvey, M. D.; Yee, G. T.; Lachgar, A. Crystal Growth&Design, 2009, 9: 1020
10. [10]
  10. Ingleson, M. J.; Mahon, M. F.; Raithby, P. R.; Weller, A. S. J. Am. Chem. Soc., 2004, 126: 4784
11. [11]
  11. Brayshaw, S. K.; Ingleson, M. J.; Green, J. C.; Raithby, P. R; Kohn, G. K.; Mcindone, J. S.; Weller, A. S. Angew. Chem. Int. Edit., 2005, 44: 6875
12. [12]
  12. Brayshaw, S. K.; Green, J. C.; Hazari, N.; Mcindoe, J. S.; Marken, F.; Raithby, P. R;Weller, A. S. Angew. Chem. Int. Edit., 2006, 45: 6005
13. [13]
  13. Brayshaw, S. K.; Ingleson, M. J.; Green, J. C.; Mcindoe, J. S.; Raithby, P. R; Kohn, G. K.; Weller, A. S. J. Am. Chem. Soc., 2006, 128: 6247
14. [14]
  14. Min s, D. M. P.; Lin, Z. Y. Z. Phys. D, 1989, 12: 53
15. [15]
  15. Lin, Z. Y.;Williams, I. D. Polyhedron, 1996, 15: 3277
16. [16]
  16. Brayshaw, S. K.; Harrison, A.; Mcindoe, J. S.; Marken, F.; Raithby, P. R.;Warren, J. E.; Weller, A. S. J. Am. Chem. Soc., 2007, 129: 1793
17. [17]
  17. Brayshaw, S. K.; Green, J. C.; Hazari, N.; Weller, A. S. Dalton Trans., 2007, 18: 1781
18. [18]
  18. Douglas, T. M.; Brayshaw, S. K.; Raithby, P. R.; Weller, A. S. Inorg. Chem., 2008, 47: 778
19. [19]
  19. Wang, Y. P.; Gu, Y. B.; Lin, M. H.; Zhang, Q. E. Chem. J. Chin. Univ., 2002, 23: 543 [王艺平,顾勇冰,林梦海, 张乾二.高等学校化学学报, 2002, 23: 543]
20. [20]
  20. Wang, X.; Lin, M. H.; Zhang, Q. E. Acta Chim. Sin., 2004, 62: 1689 [王娴,林梦海,张乾二. 化学学报, 2004, 62: 1689]
21. [21]
  21. Qiu,W. W.; Lin, M. H. Acta Phys. -Chim. Sin., 2008, 24: 1573 [邱玮玮,林梦海. 物理化学学报, 2008, 24: 1573]
22. [22]
  22. (a) Delley, B. J. Chem. Phys., 1990, 92: 508 (b) Delley, B. J. Chem. Phys., 2000, 113: 7756
23. [23]
  23. Zhang, Q. E. Journal of Xiamen University, 1981, 20: 226 [张乾二.厦门大学学报, 1981, 20: 226]
24. [24]
  24. Basson, S. S.; Leipoldt, J. G. Transit. Met. Chem., 1982, 7: 207
1. [1]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
2. [2]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
3. [3]
  Hailian Tang , Siyuan Chen , Qiaoyun Liu , Guoyi Bai , Botao Qiao , Fei Liu . Stabilized Rh/hydroxyapatite Catalyst for Furfuryl Alcohol Hydrogenation: Application of Oxidative Strong Metal-Support Interactions in Reducing Conditions. Acta Physico-Chimica Sinica, 2025, 41(4): 100036-. doi: 10.3866/PKU.WHXB202408004
4. [4]
  Jie ZHAO , Huili ZHANG , Xiaoqing LU , Zhaojie WANG . Theoretical calculations of CO₂ capture and separation by functional groups modified 2D covalent organic framework. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 275-283. doi: 10.11862/CJIC.20240213
5. [5]
  Meifeng Zhu , Jin Cheng , Kai Huang , Cheng Lian , Shouhong Xu , Honglai Liu . Classical Density Functional Theory for Understanding Electrochemical Interface. University Chemistry, 2025, 40(3): 148-152. doi: 10.12461/PKU.DXHX202405166
6. [6]
  Kaifu Zhang , Shan Gao , Bin Yang . Application of Theoretical Calculation with Fun Practice in Raman Spectroscopy Experimental Teaching. University Chemistry, 2025, 40(3): 62-67. doi: 10.12461/PKU.DXHX202404045
7. [7]
  Fei Xie , Chengcheng Yuan , Haiyan Tan , Alireza Z. Moshfegh , Bicheng Zhu , Jiaguo Yu . d带中心调控过渡金属单原子负载COF吸附O₂的理论计算研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2407013-. doi: 10.3866/PKU.WHXB202407013
8. [8]
  Lubing Qin , Fang Sun , Meiyin Li , Hao Fan , Likai Wang , Qing Tang , Chundong Wang , Zhenghua Tang . 原子精确的(AgPd)₂₇团簇用于硝酸盐电还原制氨：一种配体诱导策略来调控金属核. Acta Physico-Chimica Sinica, 2025, 41(1): 2403008-. doi: 10.3866/PKU.WHXB202403008
9. [9]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
10. [10]
  Xiaochen Zhang , Fei Yu , Jie Ma . 多角度数理模拟在电容去离子中的前沿应用. Acta Physico-Chimica Sinica, 2024, 40(11): 2311026-. doi: 10.3866/PKU.WHXB202311026
11. [11]
  Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
12. [12]
  Geyang Song , Dong Xue , Gang Li . Recent Advances in Transition Metal-Catalyzed Synthesis of Anilines from Aryl Halides. University Chemistry, 2024, 39(2): 321-329. doi: 10.3866/PKU.DXHX202308030
13. [13]
  Jing WU , Puzhen HUI , Huilin ZHENG , Pingchuan YUAN , Chunfei WANG , Hui WANG , Xiaoxia GU . Synthesis, crystal structures, and antitumor activities of transition metal complexes incorporating a naphthol-aldehyde Schiff base ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2422-2428. doi: 10.11862/CJIC.20240278
14. [14]
  Tingting XU , Wenjing ZHANG , Yongbo SONG . Research advances of atomic precision coinage metal nanoclusters in tumor therapy. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2275-2285. doi: 10.11862/CJIC.20240229
15. [15]
  Xiaofeng Zhu , Bingbing Xiao , Jiaxin Su , Shuai Wang , Qingran Zhang , Jun Wang . Transition Metal Oxides/Chalcogenides for Electrochemical Oxygen Reduction into Hydrogen Peroxides. Acta Physico-Chimica Sinica, 2024, 40(12): 2407005-. doi: 10.3866/PKU.WHXB202407005
16. [16]
  Lu XU , Chengyu ZHANG , Wenjuan JI , Haiying YANG , Yunlong FU . Zinc metal-organic framework with high-density free carboxyl oxygen functionalized pore walls for targeted electrochemical sensing of paracetamol. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 907-918. doi: 10.11862/CJIC.20230431
17. [17]
  Danqing Wu , Jiajun Liu , Tianyu Li , Dazhen Xu , Zhiwei Miao . Research Progress on the Simultaneous Construction of C—O and C—X Bonds via 1,2-Difunctionalization of Olefins through Radical Pathways. University Chemistry, 2024, 39(11): 146-157. doi: 10.12461/PKU.DXHX202403087
18. [18]
  Huan LI , Shengyan WANG , Long Zhang , Yue CAO , Xiaohan YANG , Ziliang WANG , Wenjuan ZHU , Wenlei ZHU , Yang ZHOU . Growth mechanisms and application potentials of magic-size clusters of groups Ⅱ-Ⅵ semiconductors. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1425-1441. doi: 10.11862/CJIC.20240088
19. [19]
  Zitong Chen , Zipei Su , Jiangfeng Qian . Aromatic Alkali Metal Reagents: Structures, Properties and Applications. University Chemistry, 2024, 39(8): 149-162. doi: 10.3866/PKU.DXHX202311054
20. [20]
  Zuozhong Liang , Lingling Wei , Yiwen Cao , Yunhan Wei , Haimei Shi , Haoquan Zheng , Shengli Gao . Exploring the Development of Undergraduate Scientific Research Ability in Basic Course Instruction: A Case Study of Alkali and Alkaline Earth Metal Complexes in Inorganic Chemistry. University Chemistry, 2024, 39(7): 247-263. doi: 10.3866/PKU.DXHX202310103

Get Citation

PDF

XML

Metrics

PDF Downloads(1202)
Abstract views(3027)
HTML views(7)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142