Citation: Huang Min, Xu Chang, Cheng Longjiu. Density Functional Theory Studies of the Binary Systems[B_xAl₁₃_-x]^- (x=0～13)[J]. Acta Chimica Sinica, ;2016, 74(9): 758-763. doi: 10.6023/A16050230 shu

Density Functional Theory Studies of the Binary Systems[B_xAl₁₃_-x]^- (x=0～13)

1.
School of Chemistry and Chemical Engineering, Anhui University, Hefei 260301

Corresponding author: Cheng Longjiu, clj@ustc.edu
Received Date: 11 May 2016

Fund Project: National Natural Science Foundation of China 21273008National Natural Science Foundation of China 21573001

Figures(5)

In this paper, the global minimum search and structural optimization for the B-Al binary clusters [B_xAl₁₃_-_x]^- (x=0～13) are performed using the genetic algorithm (GA) method coupled with density functional theory (DFT). The effects of composition on the atomic structures, electronic properties including the energy gaps and vertical detachment energies of B-Al binary clusters are discussed. The results distinctly reveal a three dimensional (3D) to (quasi-)planar (2D) structural transition as a function of x upon increasing the number of boron atoms. When x is in the range of 0 to 7, the clusters are Al-rich and the B-Al binary systems maintain the 3D structure. Whereas, the binary system trends to be quasi-planar structure, and the critical B:Al ratios for the 2D-3D transition are between x=7 and 8. To study the stability of the [B_xAl_13-x]^- clusters, we defined the relative energy (E_rel=E([B_xAl₁₃_-x]^-)-xE(B₁₃^-)/13–yE(Al₁₃^-)/13), where the cluster with a more negative E_rel is more stable. At x=1, E_rel is the most negative, indicating the highest stability. In order to further understand the stability of clusters, the vertical detachment energies (VDE) and the HOMO-LUMO energy gaps (E_H-L) of [B_xAl₁₃_-_x]^- (x=0～13) clusters are also calculated. The results show that the energy decreases with the increasing number of B atoms, indicating a lower stability. The largest E_H-L of BAl₁₂^- cluster indicates that it is the most stable among all the series of this clusters. Molecular orbitals (MO) of BAl₁₂^- cluster are analyzed and the result shows that the electronic shells of 1s² and 1p⁶ are virtually unchanged when the central Al atom is replaced by the B atom. It also indicates that the electron shell closing model could be regarded as a simple but valid tool for explaining the structures and stabilities of metal clusters. Chemical bonding analysis by Adaptive Natural Density Partitioning (AdNDP) method for the B₁₃^- cluster reveals that it is a π-antiaromatic system with 8 delocalized π-electrons.
- density functional theory,
- [B_xAl₁₃_-x]^- (x=0～13) clusters,
- optimization,
- molecular orbitals,
- adaptive natural density partitioning
1. [1]
  Yuan, Y.; Cheng, L.-J. J. Chem. Phys. 2012, 137, 044308. doi: 10.1063/1.4738957
2. [2]
  Kiran, B.; Gopa Kumar, G.; Nguyen, M. T.; Kandalam, A. K.; Jena, P. Inorg. Chem. 2009, 48, 9965. doi: 10.1021/ic901410h
3. [3]
  Aguado, A.; López, J. M. J. Chem. Phys. 2009, 130, 064704. doi: 10.1063/1.3075834
4. [4]
  Zhai, H.-J.; Zhao, Y.-F.; Li, W.-L.; Chen, Q.; Bai, H.; Hu, H.-S.; Piazza, Z. A.; Tian, W.-J.; Lu, H.-G.; Wu, Y.-B. Nat. Chem. 2014, 6, 727.
5. [5]
  Li, L.; Xu, C.; Jin, B.-K.; Cheng, L.-J. J. Chem. Phys. 2013, 139, 174310. doi: 10.1063/1.4827517
6. [6]
  Li, L.; Xu, C.; Cheng, L.-J. Comput. Theor. Chem. 2013, 1021, 144. doi: 10.1016/j.comptc.2013.07.001
7. [7]
  Deshpande, M.; Kanhere, D.; Vasiliev, I.; Martin, R. M. Phys. Rev. B 2003, 68, 035428. doi: 10.1103/PhysRevB.68.035428
8. [8]
  Wang, L.; Zhao, J.-J.; Wang, Y.-J.; Gong, Z.-Z.; Guo, Y.-X.; Wei, D.-Q. J. At. Mol. Phys. 2007, 24, 559 (in Chinese).
9. [9]
  Liu, L.-R.; Lei, X.-L.; Chen, H.; Zhu, H.-J. Acta Phys. Sin. 2009, 58, 5355 (in Chinese).
10. [10]
  Lei, X.-L.; Zhu, H.-J.; Wang, X.-M.; Luo, Y.-H. Acta Phys.-Chim. Sin. 2008, 24, 1655 (in Chinese).
11. [11]
  Alexandrova, A. N.; Boldyrev, A. I.; Zhai, H.-J.; Wang, L.-S. Coord. Chem. Rev. 2006, 250, 2811. doi: 10.1016/j.ccr.2006.03.032
12. [12]
  Zhai, H.-J.; Alexandrova, A. N.; Birch, K. A.; Boldyrev, A. I.; Wang, L.-S. Angew. Chem., Int. Ed. 2003, 42, 6004. doi: 10.1002/(ISSN)1521-3773
13. [13]
  Popov, I. A.; Popov, V. F.; Bozhenko, K. V.; Černušák, I.; Boldyrev, A. I. J. Chem. Phys. 2013, 139, 114307. doi: 10.1063/1.4820878
14. [14]
  Galeev, T. R.; Ivanov, A. S.; Romanescu, C.; Li, W.-L.; Bozhenko, K. V.; Wang, L.-S.; Boldyrev, A. I. Phys. Chem. Chem. Phys. 2011, 13, 8805. doi: 10.1039/c1cp20359b
15. [15]
  Kawamata, H.; Negishi, Y.; Nakajima, A.; Kaya, K. Chem. Phys. Lett. 2001, 337, 255. doi: 10.1016/S0009-2614(01)00198-1
16. [16]
  Zhu, Z. Z.; Bo, T. Solid State Commun. 1998, 108, 891. doi: 10.1016/S0038-1098(98)00400-1
17. [17]
  Ashman, C.; Khanna, S.; Liu, F.; Jena, P.; Kaplan, T.; Mostoller, M. Phys. Rev. B 1997, 55, 15868. doi: 10.1103/PhysRevB.55.15868
18. [18]
  Burgert, R.; Stokes, S. T.; Bowen, K. H.; Schnöckel, H. J. Am. Chem. Soc. 2006, 128, 7904. doi: 10.1021/ja060613x
19. [19]
  Jung, J.; Kim, J. C.; Han, Y.-K. Phys. Rev. B 2005, 72, 155439. doi: 10.1103/PhysRevB.72.155439
20. [20]
  Li, C.-L.; Duan, H.-M.; Mardan, K. Acta Phys. Sin. 2013, 19, 178 (in Chinese).
21. [21]
  Bergeron, D.; Roach, P.; Castleman, A.; Jones, N.; Khanna, S. Science 2005, 307, 231. doi: 10.1126/science.1105820
22. [22]
  Bergeron, D. E.; Castleman, A. W.; Morisato, T.; Khanna, S. N. Science 2004, 304, 84. doi: 10.1126/science.1093902
23. [23]
  Li, S. F.; Gong, X. G. Phys. Rev. B 2004, 70, 075404.
24. [24]
  Zope, R. R.; Baruah, T. Phys. Rev. A 2001, 64, 053202. doi: 10.1103/PhysRevA.64.053202
25. [25]
  Gong, X. G.; Kumar, V. Phys. Rev. Lett. 1993, 70, 2078. doi: 10.1103/PhysRevLett.70.2078
26. [26]
  Li, X.; Wang, L.-S. Phys. Rev. B 2002, 65, 153404. doi: 10.1103/PhysRevB.65.153404
27. [27]
  Pal, R.; Cui, L.-F.; Bulusu, S.; Zhai, H.-J.; Wang, L.-S.; Zeng, X. C. J. Chem. Phys. 2008, 128, 024305. doi: 10.1063/1.2805386
28. [28]
  Wang, L.; Zhao, J.-J.; Zhou, Z.; Zhang, S. B.; Chen, Z.-F. J. Comput. Chem. 2009, 30, 2509. doi: 10.1002/jcc.v30:15
29. [29]
  Tang, D.-Y.; Huang, X.-N.; Zou, T.; Jin, C.; Hu, J.-P.; Fu, Q.-C. Acta Phys.-Chim. Sin. 2010, 26, 34 (in Chinese).
30. [30]
  Tang, D.-Y.; Jin, C.; Zou, T.; Huang, X.-N. Acta Chim. Sinica 2009, 67, 1539 (in Chinese).
31. [31]
  Lei, X.-L. J. Clust. Sci. 2011, 22, 159. doi: 10.1007/s10876-011-0370-x
32. [32]
  Tang, X.; Lȕ, H.-F.; Ma, C.-L.; Zhao, J.-J.; Zhang, Q.-Y. Acta Phys. Sin. 2008, 57, 7806 (in Chinese).
33. [33]
  Zhao, J.-J.; Buldum, A.; Han, J.; Lu, J. P. Phys. Rev. Lett. 2000, 85, 1706. doi: 10.1103/PhysRevLett.85.1706
34. [34]
  Ran, R.-X.; Fan, X.-L.; Liu, Y.; Yang, Y.-L. Acta Chim. Sinica 2013, 71, 829 (in Chinese). doi: 10.6023/A13010083
35. [35]
  Cheng, L.-J. J. Chem. Phys. 2012, 136, 104301. doi: 10.1063/1.3692183
36. [36]
  Li, L.-F.; Cheng, L.-J. J. Chem. Phys. 2013, 138, 094312. doi: 10.1063/1.4793707
37. [37]
  Tian, Z.-M.; Cheng, L.-J. Phys. Chem. Chem. Phys. 2015, 17, 13421. doi: 10.1039/C5CP01863C
38. [38]
  Zhao, J.-J.; Shi, R.-L.; Sai, L.-W.; Huang, X.-M.; Su, Y. Mol. Simulat. 2016, 42, 809. doi: 10.1080/08927022.2015.1121386
39. [39]
  Frisch, M.; Trucks, G.; Schlegel, H. B.; Scuseria, G.; Robb, M.; Cheeseman, J.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. Gaussian 09, Gaussian Inc., Wallingford, CT, 2009.
40. [40]
  Varetto, U. MOLEKEL, 5.4.0.8, Swiss National Supercomputing Centre, Manno, Switzerland, 2009.
41. [41]
  Hong, L.; Wang, H.-L.; Cheng, J.-X.; Huang, X.-M.; Sai, L.-W.; Zhao, J.-J. Comput. Theor. Chem. 2012, 993, 36. doi: 10.1016/j.comptc.2012.05.027
42. [42]
  Smith, J. C.; Reber, A. C.; Khanna, S. N.; Castleman Jr., A. W. J. Phys. Chem. A 2014, 118, 8485. doi: 10.1021/jp501934t
43. [43]
  Zhang, M.; Zhang, J.; Feng, X.; Zhang, H.; Zhao, L.; Luo, Y.; Cao, W. J. Phys. Chem. A 2013, 117, 13025. doi: 10.1021/jp410489g
44. [44]
  Gu, J.-B.; Yang, X.-D.; Wang, H.-Q.; Li, H.-F. Chinese Phys. B 2012, 21, 043102. doi: 10.1088/1674-1056/21/4/043102
45. [45]
  Cheng, L.-J.; Zhang, X.-Z.; Jin, B.-K.; Yang, J.-L. Nanoscale 2014, 6, 12440. doi: 10.1039/C4NR03550J
46. [46]
  Zhai, H.-J.; Kiran, B.; Li, J.; Wang, L.-S. Nat. Mater. 2003, 2, 827. doi: 10.1038/nmat1012
47. [47]
  Zubarev, D. Y.; Boldyrev, A. I. J. Org. Chem. 2008, 73, 9251. doi: 10.1021/jo801407e
48. [48]
  Zubarev, D. Y.; Boldyrev, A. I. Phys. Chem. Chem. Phys. 2008, 10, 5207. doi: 10.1039/b804083d
49. [49]
  Zubarev, D. Y.; Boldyrev, A. I. J. Phys. Chem. A 2008, 113, 866.
50. [50]
  Pick, Š. Collect. Czech. Chem. 1988, 53, 1607. doi: 10.1135/cccc19881607
51. [51]
  Figeys, H. Tetrahedron 1970, 26, 5225. doi: 10.1016/S0040-4020(01)98731-9
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]
  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
3. [3]
  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
4. [4]
  Jia Yao , Xiaogang Peng . Theory of Macroscopic Molecular Systems: Theoretical Framework of the Physical Chemistry Course in the Chemistry “101 Plan”. University Chemistry, 2024, 39(10): 27-37. doi: 10.12461/PKU.DXHX202408117
5. [5]
  Lisen Sun , Yongmei Hao , Zhen Huang , Yongmei Liu . Experimental Teaching Design for Viscosity Measurement Serves the Optimization of Operating Conditions for Kitchen Waste Treatment Equipment. University Chemistry, 2024, 39(2): 52-56. doi: 10.3866/PKU.DXHX202307063
6. [6]
  Jin Tong , Shuyan Yu . Crystal Engineering for Supramolecular Chirality. University Chemistry, 2024, 39(3): 86-93. doi: 10.3866/PKU.DXHX202308113
7. [7]
  Yanhui XUE , Shaofei CHAO , Man XU , Qiong WU , Fufa WU , Sufyan Javed Muhammad . Construction of high energy density hexagonal hole MXene aqueous supercapacitor by vacancy defect control strategy. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1640-1652. doi: 10.11862/CJIC.20240183
8. [8]
  Zhao Lu , Hu Lv , Qinzhuang Liu , Zhongliao Wang . Modulating NH₂ Lewis Basicity in CTF-NH₂ through Donor-Acceptor Groups for Optimizing Photocatalytic Water Splitting. Acta Physico-Chimica Sinica, 2024, 40(12): 2405005-. doi: 10.3866/PKU.WHXB202405005
9. [9]
  Hui Li , Wei Cheng , Meng Yu , Yi Li . Improving Postgraduate Cultivation in Chemistry Discipline: A Case Study of the Chemistry Program in Jilin University. University Chemistry, 2024, 39(6): 17-22. doi: 10.3866/PKU.DXHX202403047
10. [10]
  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
11. [11]
  Kai Yang , Gehua Bi , Yong Zhang , Delin Jin , Ziwei Xu , Qian Wang , Lingbao Xing . Comprehensive Polymer Chemistry Experiment Design: Preparation and Characterization of Rigid Polyurethane Foam Materials. University Chemistry, 2024, 39(4): 206-212. doi: 10.3866/PKU.DXHX202308045
12. [12]
  Cheng PENG , Jianwei WEI , Yating CHEN , Nan HU , Hui ZENG . First principles investigation about interference effects of electronic and optical properties of inorganic and lead-free perovskite Cs₃Bi₂X₉ (X=Cl, Br, I). Chinese Journal of Inorganic Chemistry, 2024, 40(3): 555-560. doi: 10.11862/CJIC.20230282
13. [13]
  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
14. [14]
  Junjie Zhang , Yue Wang , Qiuhan Wu , Ruquan Shen , Han Liu , Xinhua Duan . Preparation and Selective Separation of Lightweight Magnetic Molecularly Imprinted Polymers for Trace Tetracycline Detection in Milk. University Chemistry, 2024, 39(5): 251-257. doi: 10.3866/PKU.DXHX202311084
15. [15]
  Tingyu Zhu , Hui Zhang , Wenwei Zhang . Exploration and Practice of Ideological and Political Education in the Course of Experiments on Chemical Functional Molecules: Synthesis and Catalytic Performance Study of Chiral Mn(III)Cl-Salen Complex. University Chemistry, 2024, 39(4): 75-80. doi: 10.3866/PKU.DXHX202311011
16. [16]
  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
17. [17]
  Yue Li , Minghao Fan , Conghui Wang , Yanxun Li , Xiang Yu , Jun Ding , Lei Yan , Lele Qiu , Yongcai Zhang , Longlu Wang . 3D layer-by-layer amorphous MoS_x assembled from [Mo₃S₁₃]^2- clusters for efficient removal of tetracycline: Synergy of adsorption and photo-assisted PMS activation. Chinese Chemical Letters, 2024, 35(9): 109764-. doi: 10.1016/j.cclet.2024.109764
18. [18]
  Yong Shu , Xing Chen , Sai Duan , Rongzhen Liao . How to Determine the Equilibrium Bond Distance of Homonuclear Diatomic Molecules: A Case Study of H₂. University Chemistry, 2024, 39(7): 386-393. doi: 10.3866/PKU.DXHX202310102
19. [19]
  Keke Han , Wenjun Rao , Xiuli You , Haina Zhang , Xing Ye , Zhenhong Wei , Hu Cai . Two new high-temperature molecular ferroelectrics [1,5-3.2.2-Hdabcni]X (X = ClO₄⁻, ReO₄⁻). Chinese Chemical Letters, 2024, 35(6): 108809-. doi: 10.1016/j.cclet.2023.108809
20. [20]
  Mianying Huang , Zhiguang Xu , Xiaoming Lin . Mechanistic analysis of Co2VO4/X (X = Ni, C) heterostructures as anode materials of lithium-ion batteries. Chinese Journal of Structural Chemistry, 2024, 43(7): 100309-100309. doi: 10.1016/j.cjsc.2023.100309

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(953)
HTML views(96)

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

Density Functional Theory Studies of the Binary Systems[BxAl13-x]- (x=0～13)

Metrics

通讯作者: 陈斌, bchen63@163.com

Density Functional Theory Studies of the Binary Systems[B_xAl₁₃_-x]^- (x=0～13)