从头计算方法比较研究B2Au4, Al2Au4和BAlAu4的几何和电子结构

doi:10.3866/PKU.WHXB201409301

Abstract

Abstract:

Au/H similarity is a hot topic in chemistry. Here, we report the theoretical prediction of new members of the Au/H analogy family: covalent B₂Au₄, ionic Al₂Au₄, and BAlAu₄. A comparative study of the geometric and electronic structures of electron-deficient B₂Au₄, Al₂Au₄, and BAlAu₄ was performed based on density and wave functional theories. Detailed orbital analyses, adaptive natural density partitioning (AdNDP), and electron localization function (ELF) analyses were performed. Ab initio theoretical evidence strongly suggests that the ground state of slightly distorted C₂B₂Au₄ is a covalent complex containing two B―Au―B three centers-two electrons (3c-2e) bonds. Unexpectedly, C_3vAl⁺(AlAu₄)^- and C_3v Al⁺(BAu₄)^- are predicted to have a salt-like composition with three X―Au―Al 3c-2e bonds (X=Al in Al₂Au₄, X=B in BAlAu₄). Al₂Au₄ and BAlAu₄ represent the first examples of bridging gold bonds in ionic-deficient systems. The adiabatic and vertical detachment energies of the anions were calculated to facilitate their future experimental characterization. Bridging gold addressed in this work provides an interesting bonding mode for covalent and ionic-deficient systems, and may aid in designing new materials and catalysts with highly dispersed Au atoms.

Key words: Boron auride, Aluminum auride, Adaptive natural density partitioning, Electron localization function, Photoelectron spectroscopy

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YAO Wen-Zhi, LU Zhang-Hui, LI Si-Dian. A Comparative Ab initio Study of the Geometric and Electronic Structures of B₂Au₄, Al₂Au₄ and BAlAu₄[J]. Acta Phys. -Chim. Sin. 2014, 30(12), 2233-2240. doi: 10.3866/PKU.WHXB201409301

References

(1) PyykkI, P.; Desclaux, J. P. Accounts Chem. Res. 1979, 12, 276. doi: 10.1021/ar50140a002
(2) PyykkI, P. Chem. Rev. 1988, 88, 563. doi: 10.1021/cr00085a006
(3) Schwerdtfeger, P.; Dolg, M.; Schwarz,W. H. E.; Bowmaker, G. A.; Boyd, P. D.W. J. Chem. Phys. 1989, 91, 1762. doi: 10.1063/1.457082
(4) Schwerdtfeger, P. Chem. Phys. Lett. 1991, 183, 457. doi: 10.1016/0009-2614(91)90409-3
(5) (a) PyykkI, P. Angew. Chem. 2002, 114, 3723. doi: 10.1002/1521-3757(20021004)114:19<3723::AID-ANGE3723>3.0.CO;2-6
(b) PyykkI, P. Angew. Chem. Int. Edit. 2002, 41, 3573.
(6) (a) Schwarz, H. Angew. Chem. 2003, 115, 4580.
(b) Schwarz, H. Angew. Chem. Int. Edit. 2003, 42, 4442.
(7) Peer,W. J.; Lagowski, J. J. J. Am. Chem. Soc. 1978, 100, 6260. doi: 10.1021/ja00487a064
(8) (a) Mudring, A. V.; Jansen, M.; Daniels, J.; Kramer, S.; Mehring, M.; Ramalho, J. P. P.; Romero, A. H.; Parrinello, M. H. Angew. Chem. 2002, 114, 128.
(b) Mudring, A. V.; Jansen, M.; Daniels, J.; Kramer, S.; Mehring, M.; Ramalho, J. P. P.; Romero, A. H.; Parrinello, M. H. Angew. Chem. Int. Edit. 2002, 41, 120.
(9) Hall, K. P.; Mingos, D. M. P. Prog. Inorg. Chem. 1984, 32, 237. doi: 10.1002/SERIES2229
(10) Lauher, J.W.;Wald, K. J. Am. Chem. Soc. 1981, 103, 7648. doi: 10.1021/ja00415a040
(11) Burdett, J. K.; Eisenstein, O.; Schweizer,W. B. Inorg. Chem. 1994, 33, 3261. doi: 10.1021/ic00093a012
(12) (a) Zhai, H. J.; Bürgel, C.; Bonacic-Koutecky, V.;Wang, L. S. J. Am. Chem. Soc. 2008, 130, 9156.
(b)Wang, X. B.;Wang, Y. L.; Yang, J.; Xing, X. P.; Li, J.; Wang, L. S. J. Am. Chem. Soc. 2009, 131, 16368. doi: 10.1021/a802408b
(13) Wang, L. S. Phys. Chem. Chem. Phys. 2010, 12, 8694. doi: 10.1039/c003886e
(14) (a) Kiran, B.; Li, X.; Zhai, H. J.; Cui, L. F.;Wang, L. S. Angew. Chem. Int. Edit. 2004, 43, 2125.
(b) Li, X.; Kiran, B.;Wang, L. S. J. Phys. Chem. A 2005, 109, 4366.
(c) Kiran, B.; Li, X.; Zhai, H. J.;Wang, L. S. J. Chem. Phys. 2006, 125, 133204.
(15) Zhai, H. J.;Wang, L. S.; Zubarev, D. Y.; Boldyrev, A. I. J. Phys. Chem. A 2006, 110, 1689. doi: 10.1021/jp0559074
(16) Zubarev, D. Y.; Boldyrev, A. I.; Li, J.; Zhai, H. J.;Wang, L. S. J. Phys. Chem. A 2007, 111, 1648.
(17) Zhai, H. J.; Miao, C. Q.; Li, S. D.;Wang, L. S. J. Phys. Chem. A 2010, 114, 12155. doi: 10.1021/jp108668t
(18) Li, D. Z.; Li, S. D. Int. J. Quantum Chem. 2011, 111, 4418. doi: 10.1002/qua.22993
(19) Yao,W. Z.; Li, D. Z.; Li, S. D. J. Comput. Chem. 2011, 32, 218. doi: 10.1002/jcc.v32.2
(20) Zubarev, D. Yu.; Li, J.;Wang, L. S.; Boldyrev, A. I. Inorg. Chem. 2006, 45, 5269. doi: 10.1021/ic060615i
(21) Chen, Q.; Zhai, H. J.; Li, S. D.;Wang, L. S. J. Chem. Phys. 2013, 138, 084306. doi: 10.1063/1.4792501
(22) Yao,W. Z.; Yao, J. B.; Li, X. B.; Li, S. D. Acta Phys. -Chim. Sin. 2013, 29, 1219. [姚文志, 姚建斌, 李新宝, 李思殿. 物理化学学报, 2013, 29, 1219.] doi: 10.3866/PKU.WHXB201303152
(23) Yao,W. Z.; Yao, J. B.; Li, S. D. Chin. J. Struct. Chem. 2012, 31, 1549.
(24) Yao,W. Z.; Liu, B. T.; Lu, Z. H.; Li, S. D. J. Phys. Chem. A 2013, 117, 5178. doi: 10.1021/jp4026656
(25) Mohr, R. R.; Lipscomb,W. N. Inorg. Chem. 1986, 25,1053. doi: 10.1021/ic00227a033
(26) Lammertsma, K.; Güner, O. F.; Drewes, R. M.; Reed, A. E.; Schleyer, P. V. R. Inorg. Chem. 1989, 28, 313. doi: 10.1021/ic00301a032
(27) Mains, G. J.; Bock, C.W.; Trachtman, M.; Finley, J.; McNamara, K.; Fisher, M.;Wociki, L. J. Phys. Chem. 1990, 94, 6996. doi: 10.1021/j100381a016
(28) (a) Zubarev, D. Y.; Boldyrev, A. I. Phys. Chem. Chem. Phys. 2008, 10, 5207. doi: 10.1039/b804083d
(b) Feng, G.; Huo, C. F.; Deng, C. M. J. Mol. Catal. A-Chem. 2009, 304, 58.
(c) Galeev, T. R.; Chen, Q.; Guo, J. C.; Bai, H.; Miao, C. Q.; Lu, H. G.; Sergeeva, A. P.; Li, D.; Boldyrev, A. I. Phys. Chem. Chem. Phys. 2011, 13, 11575
(29) (a) Silvi, B.; Savin, A. Nature 1994, 371, 683. doi: 10.1038/371683a0
(b) Becke, A.; Edgecombe, K. J. Chem. Phys. 1990, 92, 5397.
(30) Lu, H. G. In GXYZ Ver. 1.0, A Random Cartesian Coordinates Generating Program; Shanxi University: Taiyuan, 2008.
(31) (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648. doi: 10.1063/1.464913
(b) Lee, C.; Yang,W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
(32) (a) Head-Gordon, M. J.; Pople, A.; Frisch, M. J. Chem. Phys. Lett. 1988, 153, 503. doi: 10.1016/0009-2614(88)85250-3
(b) Frisch, M. J.; Head-Gordon, M.; Pople, J. A. Chem. Phys. Lett. 1990, 166, 275.
(33) (a) Cizek, J. Adv. Chem. Phys. 1969, 14, 35.
(b) Scuseria, G. E.; Schaefer, H. F. J. Chem. Phys. 1989, 90, 3700.
(c) Pople, J. A.; Head-Gordon, M.; Raghavachari, K. J. Chem. Phys. 1987, 87, 5968.
(34) (a) Dolg, M.;Wedig, U.; Stoll, H.; Preuss, H. J. Chem. Phys. 1987, 86, 866. doi: 10.1063/1.452288
(b) Martin, J. M. L.; Sundermann, A. J. Chem. Phys. 2001, 114, 3408.
(35) Kendall, R. A.; Dunning, T. H.; Harrison, R. J. J. Chem. Phys. 1992, 96, 6796. doi: 10.1063/1.462569
(36) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 09, Revision A.02; Gaussian Inc.:Wallingford, CT, 2009.
(37) Lu, T.; Chen, F.W. J. Comput. Chem. 2012, 33, 580. doi: 10.1002/jcc.v33.5
(38) Liu, J.; Aeschleman, J.; Rajan, L. M.; Che, C.; Ge, Q. in Materials Issues in a Hydrogen Economy; Jena, P., Kandalam, A., Sun, Q. Eds.;World Scientific Publishing Co. Ptc. Ltd.: Singapore, 2009; p 234.
(39) Lammertsma, K.; Ohwada, T. J. Am. Chem. Soc. 1996, 118, 7247. doi: 10.1021/ja960004x

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A Comparative Ab initio Study of the Geometric and Electronic Structures of B₂Au₄, Al₂Au₄ and BAlAu₄

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A Comparative Ab initio Study of the Geometric and Electronic Structures of B₂Au₄, Al₂Au₄ and BAlAu₄