Spectroscopic and ab initio characterization of the [ReH9]2- ion.
Spectroscopic and ab initio characterization of the [ReH9]2- ion.
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[ReH9]2- 离子的光谱和从头算表征。
DOI：
10.1021/ic0611894
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发表时间：
2006
影响因子：
4.6
通讯作者：
K. Yvon
中科院分区：
文献类型：
--
作者：
S. Parker;K. Refson;K. Williams;D. A. Braden;B. Hudson;K. Yvon
用振动光谱和密度泛函理论研究了含有D3h面盖三角形棱柱[ReH9]2-离子的氢化物配合物Ba[ReH9]的动力学和成键。红外光谱、拉曼光谱和非弹性中子散射光谱（INS）的结合首次观测到了[ReH9]2-离子的所有模式。我们证明了孤立的[ReH9]2-离子的计算不能再现INS光谱，并且必须用周期性DFT来考虑完整的单元胞才能得到可靠的结果。这被证明是长期库仑势存在的结果。电子结构分析表明，铼和氢之间的键主要是共价键。在棱柱状氢化物和钡之间有小程度的共价。反作用力对材料的稳定性至关重要；因此，它的变化可能提供了一种微调材料特性的方法。
The dynamics and bonding of the hydrido complex Ba[ReH9], containing the D3h face-capped trigonal prismatic [ReH9]2- ion, have been investigated by vibrational spectroscopy and density functional theory (DFT). The combination of infrared, Raman, and inelastic neutron-scattering (INS) spectroscopies has enabled observation of all the modes of the [ReH9]2- ion for the first time. We demonstrate that calculations of the isolated [ReH9]2- ion are unable to reproduce the INS spectrum and that the complete unit cell must be considered with periodic DFT to have reliable results. This is shown to be a consequence of the long-range Coulomb potential present. Analysis of the electronic structure shows that the bonding between the rhenium and the hydrogen is largely covalent. There is a small degree of covalency between the prism hydrides and the barium. The counterion is crucial to the stability of the materials; hence, variation of it potentially offers a method to fine-tune the properties of the material.