Spectroscopic and Ab Initio Characterization of the [ReH9]2- Ion

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• 作者：Stewart F. Parker ; Keith Refson ; Kenneth P. J. Williams ; Dale A. Braden ; Bruce S. Hudson ; Klaus Yvon
• 刊名：Inorganic Chemistry
• 出版年：2006
• 出版时间：December 25, 2006
• 年：2006
• 卷：45
• 期：26
• 页码：10951 - 10957
• 全文大小：201K
• 年卷期：v.45,no.26(December 25, 2006)
• ISSN：1520-510X

文摘

The dynamics and bonding of the hydrido complex Ba[ReH₉], containing the D_3h face-capped trigonal prismatic[ReH₉]^2- ion, have been investigated by vibrational spectroscopy and density functional theory (DFT). The combinationof infrared, Raman, and inelastic neutron-scattering (INS) spectroscopies has enabled observation of all the modesof the [ReH₉]^2- ion for the first time. We demonstrate that calculations of the isolated [ReH₉]^2- ion are unable toreproduce the INS spectrum and that the complete unit cell must be considered with periodic DFT to have reliableresults. This is shown to be a consequence of the long-range Coulomb potential present. Analysis of the electronicstructure shows that the bonding between the rhenium and the hydrogen is largely covalent. There is a smalldegree of covalency between the prism hydrides and the barium. The counterion is crucial to the stability of thematerials; hence, variation of it potentially offers a method to fine-tune the properties of the material.