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]
  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
3. [3]
  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
4. [4]
  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
5. [5]
  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
6. [6]
  Yang YANG , Pengcheng LI , Zhan SHU , Nengrong TU , Zonghua WANG . Plasmon-enhanced upconversion luminescence and application of molecular detection. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 877-884. doi: 10.11862/CJIC.20230440
7. [7]
  Yuhao SUN , Qingzhe DONG , Lei ZHAO , Xiaodan JIANG , Hailing GUO , Xianglong MENG , Yongmei GUO . Synthesis and antibacterial properties of silver-loaded sod-based zeolite. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 761-770. doi: 10.11862/CJIC.20230169
8. [8]
  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
9. [9]
  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
10. [10]
  Yufang GAO , Nan HOU , Yaning LIANG , Ning LI , Yanting ZHANG , Zelong LI , Xiaofeng LI . Nano-thin layer MCM-22 zeolite: Synthesis and catalytic properties of trimethylbenzene isomerization reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1079-1087. doi: 10.11862/CJIC.20240036
11. [11]
  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
12. [12]
  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
13. [13]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
14. [14]
  Jingqi Ma , Huangjie Lu , Junpu Yang , Liangwei Yang , Jian-Qiang Wang , Xianlong Du , Jian Lin . Rational design and synthesis of a uranyl-organic hybrid for X-ray scintillation. Chinese Journal of Structural Chemistry, 2024, 43(5): 100275-100275. doi: 10.1016/j.cjsc.2024.100275
15. [15]
  Xin Dong , Jing Liang , Zhijin Xu , Huajie Wu , Lei Wang , Shihai You , Junhua Luo , Lina Li . Exploring centimeter-sized crystals of bismuth-iodide perovskite toward highly sensitive X-ray detection. Chinese Chemical Letters, 2024, 35(6): 108708-. doi: 10.1016/j.cclet.2023.108708
16. [16]
  Xiuwen Xu , Quan Zhou , Yacong Wang , Yunjie He , Qiang Wang , Yuan Wang , Bing Chen . Expanding the toolbox of metal-free organic halide perovskite for X-ray detection. Chinese Chemical Letters, 2024, 35(9): 109272-. doi: 10.1016/j.cclet.2023.109272
17. [17]
  Hong-Jin Liao , Zhu Zhuo , Qing Li , Yoshihito Shiota , Jonathan P. Hill , Katsuhiko Ariga , Zi-Xiu Lu , Lu-Yao Liu , Zi-Ang Nan , Wei Wang , You-Gui Huang . A new class of crystalline X-ray induced photochromic materials assembled from anion-directed folding of a flexible cation. Chinese Chemical Letters, 2024, 35(8): 109052-. doi: 10.1016/j.cclet.2023.109052
18. [18]
  Xuying Yu , Jiarong Mi , Yulan Han , Cai Sun , Mingsheng Wang , Guocong Guo . A stable radiochromic semiconductive viologen-based metal–organic framework for dual-mode direct X-ray detection. Chinese Chemical Letters, 2024, 35(9): 109233-. doi: 10.1016/j.cclet.2023.109233
19. [19]
  Xin Dong , Tianqi Chen , Jing Liang , Lei Wang , Huajie Wu , Zhijin Xu , Junhua Luo , Li-Na Li . Structure design of lead-free chiral-polar perovskites for sensitive self-powered X-ray detection. Chinese Journal of Structural Chemistry, 2024, 43(6): 100256-100256. doi: 10.1016/j.cjsc.2024.100256
20. [20]
  Fei Yin , Erli Yang , Xue Ge , Qian Sun , Fan Mo , Guoqiu Wu , Yanfei Shen . Coupling WO₃₋_x dots-encapsulated metal-organic frameworks and template-free branched polymerization for dual signal-amplified electrochemiluminescence biosensing. Chinese Chemical Letters, 2024, 35(4): 108753-. doi: 10.1016/j.cclet.2023.108753

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(921)
HTML views(95)

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)