Spectroscopic and Ab initio characterization of the [ReH9] 2- ion

Stewart F. Parker, Keith Refson, Kenneth P.J. Williams, Dale A. Braden, Bruce S. Hudson, Klaus Yvon

Research output: Contribution to journalArticle

19 Scopus citations

Abstract

The dynamics and bonding of the hydrido complex Ba[ReH9], containing the D3h face-capped trigonal prismatic [ReH 9]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 [ReH 9]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.

Original languageEnglish (US)
Pages (from-to)10951-10957
Number of pages7
JournalInorganic Chemistry
Volume45
Issue number26
DOIs
StatePublished - Dec 25 2006

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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