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

doi:10.6023/A16050230

Abstract

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.

Key words: density functional theory, [B_xAl₁₃_-x]^- (x=0～13) clusters, optimization, molecular orbitals, adaptive natural density partitioning

Cite this article

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

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

References

[1] Yuan, Y.; Cheng, L.-J. J. Chem. Phys. 2012, 137, 044308.
[2] Kiran, B.; Gopa Kumar, G.; Nguyen, M. T.; Kandalam, A. K.; Jena, P. Inorg. Chem. 2009, 48, 9965.
[3] Aguado, A.; López, J. M. J. Chem. Phys. 2009, 130, 064704.
[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] Li, L.; Xu, C.; Jin, B.-K.; Cheng, L.-J. J. Chem. Phys. 2013, 139, 174310.
[6] Li, L.; Xu, C.; Cheng, L.-J. Comput. Theor. Chem. 2013, 1021, 144.
[7] Deshpande, M.; Kanhere, D.; Vasiliev, I.; Martin, R. M. Phys. Rev. B 2003, 68, 035428.
[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). (王璐, 赵纪军, 王英杰, 龚自正, 郭永新, 魏冬青, 原子与分子物理学报, 2007, 24, 559.)
[9] Liu, L.-R.; Lei, X.-L.; Chen, H.; Zhu, H.-J. Acta Phys. Sin. 2009, 58, 5355 (in Chinese). (刘立仁, 雷雪玲, 陈杭, 祝恒江, 物理学报, 2009, 58, 5355.)
[10] Lei, X.-L.; Zhu, H.-J.; Wang, X.-M.; Luo, Y.-H. Acta Phys.-Chim. Sin. 2008, 24, 1655 (in Chinese). (雷雪玲, 祝恒江, 王先明, 罗有华, 物理化学学报, 2008, 24, 1655.)
[11] Alexandrova, A. N.; Boldyrev, A. I.; Zhai, H.-J.; Wang, L.-S. Coord. Chem. Rev. 2006, 250, 2811.
[12] Zhai, H.-J.; Alexandrova, A. N.; Birch, K. A.; Boldyrev, A. I.; Wang, L.-S. Angew. Chem., Int. Ed. 2003, 42, 6004.
[13] Popov, I. A.; Popov, V. F.; Bozhenko, K. V.; ?ernušák, I.; Boldyrev, A. I. J. Chem. Phys. 2013, 139, 114307.
[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.
[15] Kawamata, H.; Negishi, Y.; Nakajima, A.; Kaya, K. Chem. Phys. Lett. 2001, 337, 255.
[16] Zhu, Z. Z.; Bo, T. Solid State Commun. 1998, 108, 891.
[17] Ashman, C.; Khanna, S.; Liu, F.; Jena, P.; Kaplan, T.; Mostoller, M. Phys. Rev. B 1997, 55, 15868.
[18] Burgert, R.; Stokes, S. T.; Bowen, K. H.; Schnöckel, H. J. Am. Chem. Soc. 2006, 128, 7904.
[19] Jung, J.; Kim, J. C.; Han, Y.-K. Phys. Rev. B 2005, 72, 155439.
[20] Li, C.-L.; Duan, H.-M.; Mardan, K. Acta Phys. Sin. 2013, 19, 178 (in Chinese). (李春丽, 段海明, 买力坦·开来木, 物理学报, 2013, 19, 178.)
[21] Bergeron, D.; Roach, P.; Castleman, A.; Jones, N.; Khanna, S. Science 2005, 307, 231.
[22] Bergeron, D. E.; Castleman, A. W.; Morisato, T.; Khanna, S. N. Science 2004, 304, 84.
[23] Li, S. F.; Gong, X. G. Phys. Rev. B 2004, 70, 075404.
[24] Zope, R. R.; Baruah, T. Phys. Rev. A 2001, 64, 053202.
[25] Gong, X. G.; Kumar, V. Phys. Rev. Lett. 1993, 70, 2078.
[26] Li, X.; Wang, L.-S. Phys. Rev. B 2002, 65, 153404.
[27] Pal, R.; Cui, L.-F.; Bulusu, S.; Zhai, H.-J.; Wang, L.-S.; Zeng, X. C. J. Chem. Phys. 2008, 128, 024305.
[28] Wang, L.; Zhao, J.-J.; Zhou, Z.; Zhang, S. B.; Chen, Z.-F. J. Comput. Chem. 2009, 30, 2509.
[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). (唐典勇, 黄雪娜, 邹婷, 金诚, 胡建平, 伏秦超, 物理化学学报2010, 26, 34.)
[30] Tang, D.-Y.; Jin, C.; Zou, T.; Huang, X.-N. Acta Chim. Sinica 2009, 67, 1539 (in Chinese). (唐典勇, 金诚, 邹婷, 黄雪娜, 化学学报, 2009, 67, 1539.)
[31] Lei, X.-L. J. Clust. Sci. 2011, 22, 159.
[32] Tang, X.; L?, H.-F.; Ma, C.-L.; Zhao, J.-J.; Zhang, Q.-Y. Acta Phys. Sin. 2008, 57, 7806 (in Chinese). (唐鑫, 吕海峰, 马春雨, 赵纪军, 张庆瑜, 物理学报 2008, 57, 7806.)
[33] Zhao, J.-J.; Buldum, A.; Han, J.; Lu, J. P. Phys. Rev. Lett. 2000, 85, 1706.
[34] Ran, R.-X.; Fan, X.-L.; Liu, Y.; Yang, Y.-L. Acta Chim. Sinica 2013, 71, 829 (in Chinese). (冉润欣, 范晓丽, 刘燕, 杨永良, 化学学报, 2013, 71, 829.)
[35] Cheng, L.-J. J. Chem. Phys. 2012, 136, 104301.
[36] Li, L.-F.; Cheng, L.-J. J. Chem. Phys. 2013, 138, 094312.
[37] Tian, Z.-M.; Cheng, L.-J. Phys. Chem. Chem. Phys. 2015, 17, 13421.
[38] Zhao, J.-J.; Shi, R.-L.; Sai, L.-W.; Huang, X.-M.; Su, Y. Mol. Simulat. 2016, 42, 809.
[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] Varetto, U. MOLEKEL,5.4.0.8, Swiss National Supercomputing Centre, Manno, Switzerland, 2009.
[41] Hong, L.; Wang, H.-L.; Cheng, J.-X.; Huang, X.-M.; Sai, L.-W.; Zhao, J.-J. Comput. Theor. Chem. 2012, 993, 36.
[42] Smith, J. C.; Reber, A. C.; Khanna, S. N.; Castleman Jr., A. W. J. Phys. Chem. A 2014, 118, 8485.
[43] Zhang, M.; Zhang, J.; Feng, X.; Zhang, H.; Zhao, L.; Luo, Y.; Cao, W. J. Phys. Chem. A 2013, 117, 13025.
[44] Gu, J.-B.; Yang, X.-D.; Wang, H.-Q.; Li, H.-F. Chinese Phys. B 2012, 21, 043102.
[45] Cheng, L.-J.; Zhang, X.-Z.; Jin, B.-K.; Yang, J.-L. Nanoscale 2014, 6, 12440.
[46] Zhai, H.-J.; Kiran, B.; Li, J.; Wang, L.-S. Nat. Mater. 2003, 2, 827.
[47] Zubarev, D. Y.; Boldyrev, A. I. J. Org. Chem. 2008, 73, 9251.
[48] Zubarev, D. Y.; Boldyrev, A. I. Phys. Chem. Chem. Phys. 2008, 10, 5207.
[49] Zubarev, D. Y.; Boldyrev, A. I. J. Phys. Chem. A 2008, 113, 866.
[50] Pick, Š. Collect. Czech. Chem. 1988, 53, 1607.
[51] Figeys, H. Tetrahedron 1970, 26, 5225.

[B_xAl₁₃_-x]^-(x=0～13)二元团簇的密度泛函理论研究

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

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Guanglong Huang, Xiao-Song Xue. Computational Study on the Mechanism of Chen’s Reagent as Trifluoromethyl Source [J]. Acta Chimica Sinica, 2024, 82(2): 132-137.
[2]	Xuefeng Liang, Jian Jing, Xin Feng, Yongze Zhao, Xinyuan Tang, Yan He, Lisheng Zhang, Huifang Li. Electronic Structure of Covalent Organic Frameworks COF66 and COF366: from Monomers to Two-Dimensional Framework [J]. Acta Chimica Sinica, 2023, 81(7): 717-724.
[3]	Wenshan Zheng, Guanbin Gao, Hao Deng, Taolei Sun. Room Temperature Synthesis and Near-infrared Fluorescence Performance Optimization of Ag₂Se@Ag₂S Core-shell Quantum Dots [J]. Acta Chimica Sinica, 2023, 81(7): 763-770.
[4]	Lei Yang, Jiaoyang Ge, Fangli Wang, Wangyang Wu, Zongxiang Zheng, Hongtao Cao, Zhou Wang, Xueqin Ran, Linhai Xie. A Theoretical Study on the Effective Reduction of Internal Reorganization Energy Based on the Macrocyclic Structure of Fluorene [J]. Acta Chimica Sinica, 2023, 81(6): 613-619.
[5]	Jie Yang, Lin Ling, Yuxue Li, Long Lu. Density Functional Theory Study on Thermal Decomposition Mechanisms of Ammonium Perchlorate [J]. Acta Chimica Sinica, 2023, 81(4): 328-337.
[6]	Shaoqin Zhang, Meiqing Li, Zhongjun Zhou, Zexing Qu. Theoretical Study on the Multiple Resonance Thermally Activated Delayed Fluorescence Process [J]. Acta Chimica Sinica, 2023, 81(2): 124-130.
[7]	Jinjing Liu, Na Yang, Li Li, Zidong Wei. Theoretical Study on the Regulation of Oxygen Reduction Mechanism by Modulating the Spatial Structure of Active Sites on Platinum^★ [J]. Acta Chimica Sinica, 2023, 81(11): 1478-1485.
[8]	Wenchao Bi, Linfeng Zhang, Jian Chen, Ruixue Tian, Hao Huang, Man Yao. Lithiation Mechanism and Performance of Monoclinic ZnP₂ Anode Materials [J]. Acta Chimica Sinica, 2022, 80(6): 756-764.
[9]	Xuefei Luan, Congzhi Wang, Liangshu Xia, Weiqun Shi. Theoretical Studies on the Interaction of Uranyl with Carboxylic Acids and Oxime Ligands [J]. Acta Chimica Sinica, 2022, 80(6): 708-713.
[10]	Luocong Wang, Zhewei Li, Caiwei Yue, Peihuan Zhang, Ming Lei, Min Pu. Theoretical Study on the Isomerization Mechanism of Azobenzene Derivatives under Electric Field [J]. Acta Chimica Sinica, 2022, 80(6): 781-787.
[11]	Yinghui Wang, Simin Wei, Jinwei Duan, Kang Wang. Mechanism of Silyl Enol Ethers Hydrogenation Catalysed by Frustrated Lewis Pairs: A Theoretical Study [J]. Acta Chimica Sinica, 2021, 79(9): 1164-1172.
[12]	Qingmin Man, Zunyun Fu, Tiantian Liu, Mingyue Zheng, Hualiang Jiang. DFT Mechanism of Cu Catalyzed Coupling Reaction to Alkyl Aryl Ethers [J]. Acta Chimica Sinica, 2021, 79(7): 948-952.
[13]	Yan Wang, Yingqi Tian, Zhong Jin, Bingbing Suo. Hartree-Fock and Density Functional Calculations on Graphics Processing Unit [J]. Acta Chimica Sinica, 2021, 79(5): 653-657.
[14]	Ruiqi Dong, Feng Wu, Ying Bai, Chuan Wu. Sodium Storage Mechanism and Optimization Strategies for Hard Carbon Anode of Sodium Ion Batteries [J]. Acta Chimica Sinica, 2021, 79(12): 1461-1476.
[15]	Yu Mohan, Cheng Yuanyuan, Liu Yajun. Mechanistic Study of Oxygenation Reaction in Firefly Bioluminescence [J]. Acta Chimica Sinica, 2020, 78(9): 989-993.

[BxAl13-x]-(x=0～13)二元团簇的密度泛函理论研究