Electronic and molecular structure of photoexcited [Ru-II(bpy)(3)](2+) probed by picosecond X-ray absorption spectroscopy

W Gawelda, M Johnson, FMF de Groot, R Abela, C Bressler, M Chergui*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

Abstract

L-2,L-3 X-ray absorption spectra of aqueous [Ru-II(bpy)(3)](2+) have been recorded in its ground and excited states, 50 ps after short pulse laser excitation. Significant changes in both the XANES (X-ray Near-Edge Absorption Structure) and the EXAFS (Extended X-ray Absorption Fine Structure) regions of the excited state complex are detected. The XANES line shapes have been quantitatively simulated using a crystal field multiplet code in trigonal symmetry. In addition, spectral changes in the EXAFS region of both ground and excited states are analyzed in order to extract structural parameters of their corresponding molecular structures. We obtain a Ru-N bond contraction by similar to 0.03 angstrom in the excited-state complex, as compared to the ground-state compound. This contraction results from electrostatic and polarization contributions, limited by steric constraints on the bpy ligands.

Original languageEnglish
Pages (from-to)5001-5009
Number of pages9
JournalJournal of the American Chemical Society
Volume128
Issue number15
DOIs
Publication statusPublished - 19 Apr 2006

Keywords

  • TRANSITION-METAL-COMPLEXES
  • NEAR-EDGE STRUCTURE
  • QUANTUM-CHEMICAL CALCULATIONS
  • LIGAND CHARGE-TRANSFER
  • EXCITED-STATES
  • POLYPYRIDINE COMPLEXES
  • COORDINATION-COMPOUNDS
  • CRYSTAL-STRUCTURES
  • SPECTRA
  • PHOTOCHEMISTRY

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