Phys. Rev. B 74, 205427 (2006) [9 pages]
Stabilization mechanism of Si12 cage clusters by encapsulation of a transition-metal atom: A density-functional theory study
Abstract
References (44)
Citing Articles
Noriyuki UchidaAdvanced Semiconductor Research Center, National Institute of Advanced Industrial Science and Technology, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8562, Japan and Institute of Applied Physics, University of Tsukuba, 1-1-1 Tenoudai, Tsukuba, Ibaraki 305–8573, JapanTakehide MiyazakiResearch Institute for Computational Sciences, National Institute of Advanced Industrial Science and Technology, 1-1-1 Umezono, Tsukuba, Ibaraki 305-8568, JapanToshihiko KanayamaAdvanced Semiconductor Research Center, National Institute of Advanced Industrial Science and Technology, 16-1 Onogawa, Tsukuba, Ibaraki 305-8569, Japan
Received 18 May 2006; revised 18 July 2006; published 22 November 2006
We systematically studied the geometrical and electronic structures of transition-metal (M)-encapsulating Si12 cage clusters, MSi12 (M=Hf, Ta, W, Re, Os, Ir, Pt, and Au), mainly focusing on their outstanding stability, using calculations based on density-functional theory. We found that the MSi12 clusters except HfSi12 belong to either of two distinct structural classes, the D6h-symmetric hexagonal prism (HP; for M=Ta, W, Re, and Os; total number of valence electrons per cluster, N , ranging from 53 to 56) and less-symmetric four pentagonal face (FPF; M=Re, Os, Ir, Pt, and Au; N ranging from 55 to 59) structures. The HP structure is particularly stabilized at N=54, which is understood in terms of the electronic shell closure of the M atoms due to the 18-electron rule, and the geometrical symmetry is maintained for N=53, 55, and 56 by the covalent bonding between the M atom and the Si cage accompanied by the cage-to-M charge transfer. The FPF structure is lowest in energy for N=56 and is maintained by the same covalent-bond/charge-transfer mechanism for other values of N. We propose that all these results originate from the electronic "rigidness" of the HP and FPF Si cages against the variation of N, which is the leading factor governing the stability of MSi12.
©2006 The American Physical Society
| URL: |
http://link.aps.org/doi/10.1103/PhysRevB.74.205427
|
| DOI: |
10.1103/PhysRevB.74.205427 |
| PACS: |
36.40.Qv;
31.10.+z;
61.48.+c;
31.15.Ew
|
| KEYWORDS: |
hafnium compounds,
tantalum compounds,
tungsten compounds,
rhenium compounds,
osmium compounds,
iridium compounds,
platinum compounds,
gold compounds,
molecular clusters,
density functional theory,
valency,
band structure,
bonds (chemical),
charge exchange
|
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