1. Experimental and Theoretical High-Energy-Resolution X-ray Absorption Spectroscopy: Implications for the Investigation of the Entatic State
- Author
-
Sonja Herres-Pawlis, Patrick Müller, Uwe Gerstmann, Wolf Gero Schmidt, Matthias Bauer, N. J. Vollmers, Martin Rohrmüller, and Alexander Hoffmann
- Subjects
X-ray absorption spectroscopy ,010304 chemical physics ,chemistry.chemical_element ,Entatic state ,010402 general chemistry ,01 natural sciences ,Molecular physics ,Copper ,Spectral line ,0104 chemical sciences ,Inorganic Chemistry ,Crystallography ,chemistry ,Distortion ,0103 physical sciences ,Density functional theory ,Physical and Theoretical Chemistry ,Spectroscopy ,Absorption (electromagnetic radiation) - Abstract
High-energy-resolution-fluorescence-detected X-ray absorption near-edge structure (HERFD-XANES) spectroscopy is shown to be a sensitive tool to investigate the electronic changes of copper complexes induced by geometric distortions caused by the ligand backbone as a model for the entatic state. To fully exploit the information contained in the spectra gained by the high-energy-resolution technique, (time-dependent) density functional theory calculations based on plane-wave and localized orbital basis sets are performed, which in combination allow the complete spectral range from the prepeak to the first resonances above the edge step to be covered. Thus, spectral changes upon oxidation and geometry distortion in the copper N-(1,3-dimethylimidazolidin-2-ylidene)quinolin-8-amine (DMEGqu) complexes [CuI(DMEGqu)2](PF6) and [CuII(DMEGqu)2](OTf)2·MeCN can be accessed.
- Published
- 2016