L-edge XANES analysis of photoexcited metal complexes in solution

Renske M. Van der Veen, Joshua J. Kas, Christopher J. Milne, Van Thai Pham, Amal El Nahhas, Frederico A. Lima, Dimali A. Vithanage, John J. Rehr, Rafael Abela, Majed Chergui

Research output: Contribution to journalArticlepeer-review


Ultrafast X-ray absorption spectroscopy is a powerful tool to observe electronic and geometric structures of short-lived reaction intermediates. The ab initiofeff9 code is applied to simulate the Pt L3-edge XANES spectrum of the photocatalytic diplatinum molecule [Pt2(P2O5H2)4]4− and the photo-induced changes that occur therein. The spectra are interpreted within a XAFS-like scattering theoretical framework (bound-continuum transitions) or in terms of a final-state local l-projected density of states (LDOS) (bound-bound transitions). By using a novel Bayesian fitting procedure, we show that the ground-state structures obtained independently from the XANES and EXAFS regions of the spectrum are in good agreement with each other. The semi-quantitative result obtained for the Pt-Pt contraction in the excited state is in line with recently published values. The improved theoretical treatment of inelastic losses has shown to result in more accurate peak positions in the above-continuum region of the spectrum which is an important prerequisite for obtaining quantitative structural information from (time-resolved) XANES spectra.

Original languageEnglish (US)
Pages (from-to)5551-5561
Number of pages11
JournalPhysical Chemistry Chemical Physics
Issue number21
StatePublished - 2010
Externally publishedYes

ASJC Scopus subject areas

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry


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