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X-ray Absorption Spectroscopy of Ground and Excited Rhenium-Carbonyl-Diimine Complexes: Evidence for a Two-Center Electron Transfer
- Source :
- The Journal of Physical Chemistry A, The journal of physical chemistry. A
- Publication Year :
- 2013
-
Abstract
- Steady-state and picosecond time-resolved X-ray absorption spectroscopy is used to study the ground and lowest triplet states of [ReX(CO)(3)(bpy)](n+), X = Etpy (n = 1), Cl, or Br (n = 0). We demonstrate that the transient spectra at both the Re L(3)- and Br K-edges show the emergence of a pre-edge feature, absent in the ground-state spectrum, which is associated with the electron hole created in the highest occupied molecular orbital following photoexcitation. Importantly, these features have the same dynamics, confirming previous predictions that the low-lying excited states of these complexes involve a two-center charge transfer from both the Re and the ligand, X. We also demonstrate that the DFT optimized ground and excited structures allow us to reproduce the experimental XANES and EXAFS spectra. The ground-state structural refinement shows that the Br atom contributes very little to the latter, whereas the Re-C-O scattering paths are dominant due to the so-called focusing effect. For the excited-state spectrum, the Re-X bond undergoes one of the largest changes but still remains a weak contribution to the photoinduced changes of the EXAFS spectrum.
- Subjects :
- X-ray absorption spectroscopy
Absorption spectroscopy
Extended X-ray absorption fine structure
Chemistry
02 engineering and technology
010402 general chemistry
021001 nanoscience & nanotechnology
01 natural sciences
XANES
3. Good health
0104 chemical sciences
Photoexcitation
Electron transfer
Crystallography
Excited state
Physical and Theoretical Chemistry
Atomic physics
0210 nano-technology
HOMO/LUMO
Subjects
Details
- Volume :
- 117
- Database :
- OpenAIRE
- Journal :
- The Journal of Physical Chemistry A
- Accession number :
- edsair.doi.dedup.....e7ed0ed705dae1f599a7b39ea2c97a39