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http://dx.doi.org/10.5012/bkcs.2012.33.1.153

Electronic and Bonding Properties of BaGaGeH: Hydrogen-induced Metal-insulator Transition from the AlB2-type BaGaGe Precursor  

Kang, Dae-Bok (Department of Chemistry, Kyungsung University)
Publication Information
Bulletin of the Korean Chemical Society / v.33, no.1, 2012 , pp. 153-158 More about this Journal
Abstract
The hydrogenation of $AlB_2$-type BaGaGe exhibits a metal to insulator (MI) transition, inducing a puckering distortion of the original hexagonal [GaGe] layers. We investigate the electronic structure changes associated with the hydrogen-induced MI transition, using extended H$\ddot{u}$ckel tight-binding band calculations. The results indicate that hydrogen incorporation in the precursor BaGaGe is characterized by an antibonding interaction of $\pi$ on GaGe with hydrogen 1s and the second-order mixing of the singly occupied antibonding $\pi^*$ orbital into it, through Ga-H bond formation. As a result, the fully occupied bonding $\pi$ band in BaGaGe changes to a weakly dispersive band with Ge pz (lone pair) character in the hydride, which becomes located just below the Fermi level. The Ga-Ge bonds within a layered polyanion are slightly weakened by hydrogen incorporation. A rationale for this is given.
Keywords
Metal hydride; Zintl phase; Electronic structure;
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1 Albright, T. A.; Burdett, J. K.; Whangbo, M.-H. Orbital Interactions in Chemistry; Wiley-Interscience: New York, 1985; Chap. 3.
2 Zintl, E. Angew. Chem. 1939, 52, 1.   DOI
3 Kauzlarich, S. M., Ed.; Chemistry, Structure and Bonding of Zintl Phases and Ions; VCH Publishers: New York, 1996
4 Imai, M.; Abe, E.; Ye, J.; Nishida, K.; Kimura, T.; Honma, K.; Abe, H.; Kitazawa, H. Phys. Rev. Lett. 2001, 87, 077003.   DOI   ScienceOn
5 Imai, M.; Nishida, K.; Kimura, T.; Abe, H. Appl. Phys. Lett. 2002, 80, 1019.   DOI   ScienceOn
6 Imai, M.; Nishida, K.; Kimura, T.; Kitazawa, H.; Abe, H.; Kito, H.; Yosii, K. Physica C 2002, 382, 361.   DOI   ScienceOn
7 Lorenz, B.; Lenzi, J.; Cmaidalka, J.; Meng, R. L.; Sun, Y. Y.; Xue, Y. Y.; Chu, C. W. Physica C 2002, 383, 191.   DOI   ScienceOn
8 Imai, M.; Nishida, K.; Kimura, T.; Abe, H. Physica C 2002, 377, 96.   DOI   ScienceOn
9 An, J. M.; Pickett, W. E. Phys. Rev. Lett. 2001, 86, 4366.   DOI   ScienceOn
10 Giantomassi, M.; Boeri, L.; Bachelet, G. B. Phys. Rev. B 2005, 72, 224512.   DOI   ScienceOn
11 Mazin, I. I.; Papaconstantopoulos, D. A. Phys. Rev. B 2004, 69, 180512(R).   DOI
12 Huang, G. Q.; Chen, L. F.; Liu, M.; Xing, D. Y. Phys. Rev. B 2004, 69, 064509.   DOI   ScienceOn
13 Bjorling, T.; Noreus, D.; Jansson, K.; Andersson, M.; Leonova, E.; Eden, M.; Halenius, U.; Häussermann, U. Angew. Chem., Int. Ed. 2005, 44, 7269.   DOI   ScienceOn
14 Hoekstra, A. F. T.; Roy, A. S.; Rosenbaum, T. F.; Griessen, R.; Wijngaarden, R. J.; Koeman, N. J. Phys. Rev. Lett. 2001, 86, 5349.   DOI   ScienceOn
15 Evans, M. J.; Holland, G. P.; Garcia-Garcia, F. J.; Häussermann, U. J. Am. Chem. Soc. 2008, 130, 12139.   DOI   ScienceOn
16 Whangbo, M.-H.; Hoffmann, R. J. Am. Chem. Soc. 1978, 100, 6093.   DOI
17 Whangbo, M.-H.; Hoffmann, R.; Woodward, R. B. Proc. R. Soc. A 1979, 366, 23.   DOI
18 Ren, J.; Liang, W.; Whang, M.-H. CAESAR Program; PrimeColor Software Inc.: Cary, NC, 1998.
19 Pauling, L. The Nature of the Chemical Bond; Cornell University Press: Ithaca, NY, 1960.
20 Bjorling, T.; Noreus, D.; Haussermann, U. J. Am. Chem. Soc. 2006, 128, 817.   DOI   ScienceOn
21 Nagamatsu, J.; Nakagawa, N.; Muranaka, T.; Zenitani, Y.; Akimitsu, J. Nature 2001, 410, 63.   DOI   ScienceOn