Inelastic Neutron Scattering and Raman Spectroscopies and Periodic DFT Studies of Rb2PtH6 and Rb2PtD6
- 25 August 2003
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 125 (38), 11656-11661
- https://doi.org/10.1021/ja034323h
Abstract
The present work has provided a complete set of assignments for the vibrational spectrum of Rb2PtH6 and Rb2PtD6. To confirm the assignments, a periodic density functional theory (DFT) code has been applied to the analysis of the inelastic neutron scattering (INS) spectrum of an ionic material for the first time. The work has also provided an explanation for the unusual infrared spectrum of the potassium salt. The most significant aspect of the work is the use of the momentum transfer information provided by an INS chopper spectrometer. The straightforward method employed for the analysis of the data is applicable to any molecular system (organic or inorganic) and demonstrates the potential of these instruments for chemistry. Periodic DFT was also used to study the other A2PtH6 (A = alkali metal) including, the at present, unknown Li salt, which is found to be stable. The DFT studies have also highlighted the crucial role of the cation in removing charge from the transition metal and “hydride” ligand. It is suggested that this is a general occurrence.Keywords
This publication has 19 references indexed in Scilit:
- Vibrational spectroscopy of tetrahedral ternary metal hydrides: Mg2NiH4, Rb3ZnH5 and their deuteridesElectronic supplementary information (ESI) available: Force constants for the [ZnH4]2– ion in D2d symmetry (Table S1) and the [NiH4]2– ion in C1 symmetry (Table S2). See http://www.rsc.org/suppdata/cp/b1/b109975b/Physical Chemistry Chemical Physics, 2002
- From molecules to solids with the DMol3 approachThe Journal of Chemical Physics, 2000
- Stabilization of Electron-Dense Palladium−Hydrido Complexes in Solid-State HydridesJournal of the American Chemical Society, 2000
- New Ternary Alkali-Metal−Transition-Metal Hydrides Synthesized at High Pressures: Characterization and PropertiesChemistry of Materials, 1998
- Shell: a code for lattice dynamics and structure optimisation of ionic crystalsComputer Physics Communications, 1998
- Darstellung, 195Pt‐NMR‐, IR‐ und Raman‐Spektren sowie Normalkoordinatenanalyse der Komplexionen [PtHnD6−n]2−, n = 0–6Zeitschrift für anorganische und allgemeine Chemie, 1997
- Hochdrucksynthese und Struktur von Rb2PtH6 und Cs2PtH6, ternären Hydriden mit K2PtCl6‐StrukturZeitschrift für anorganische und allgemeine Chemie, 1995
- High‐Pressure Synthesis of K2PtH6, a Saltlike Hydride with the K2PtCl6 StructureAngewandte Chemie International Edition in English, 1994
- Use of a rapid scanning stigmatic Raman imaging spectrograph in the industrial environmentJournal of Raman Spectroscopy, 1994
- Neutron scattering lengths and cross sectionsNeutron News, 1992