Issue 21, 2010
From the journal:

Physical Chemistry Chemical Physics

L-edge XANES analysis of photoexcited metal complexes in solution

Renske M. van der Veen,*ab   Joshua J. Kas,c   Christopher J. Milne,b   Van-Thai Pham,b   Amal El Nahhas,b   Frederico A. Lima,b   Dimali A. Vithanage,b   John J. Rehr,c   Rafael Abelaa  and  Majed Chergui*b  

* Corresponding authors

a Paul Scherrer Institute, Swiss Light Source, Switzerland
E-mail: renske.vanderveen@psi.ch

b Ecole Polytechnique Fédérale de Lausanne, Switzerland
E-mail: majed.chergui@epfl.ch

c Department of Physics, University of Washington, Seattle, USA

Abstract

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.

Graphical abstract: L-edge XANES analysis of photoexcited metal complexes in solution

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Article information

DOI
https://doi.org/10.1039/B927033G
Article type
Paper
Submitted
22 Dec 2009
Accepted
17 Feb 2010
First published
17 Mar 2010

Phys. Chem. Chem. Phys., 2010,12, 5551-5561

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L-edge XANES analysis of photoexcited metal complexes in solution

R. M. van der Veen, J. J. Kas, C. J. Milne, V. Pham, A. E. Nahhas, F. A. Lima, D. A. Vithanage, J. J. Rehr, R. Abela and M. Chergui, Phys. Chem. Chem. Phys., 2010, 12, 5551 DOI: 10.1039/B927033G

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