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L-edge XANES analysis of photoexcited metal complexes in solution

Van der Veen, Renske M.; Kas, Joshua J.; Milne, Christopher J.; Nahhas, Amal El LU ; Lima, Frederico A.; Vithanage, Dimali A. LU ; Rehr, John J.; Abela, Rafael; Chergui, Majed and Pham, Van-Thai LU (2010) In Physical Chemistry Chemical Physics 12(21). p.5551-5561
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... (More)

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.

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author
publishing date
type
Contribution to journal
publication status
published
subject
in
Physical Chemistry Chemical Physics
volume
12
issue
21
pages
11 pages
publisher
Royal Society of Chemistry
external identifiers
  • scopus:77952907292
ISSN
1463-9076
DOI
10.1039/b927033g
language
English
LU publication?
no
id
503002e0-8c1c-4e84-8aef-58a585704152
date added to LUP
2019-06-30 09:57:11
date last changed
2019-07-15 09:50:07
@article{503002e0-8c1c-4e84-8aef-58a585704152,
  abstract     = {<p>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 L<sub>3</sub>-edge XANES spectrum of the photocatalytic diplatinum molecule [Pt<sub>2</sub>(P<sub>2</sub>O<sub>5</sub>H<sub>2</sub>)<sub>4</sub>]<sup>4−</sup> 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.</p>},
  author       = {Van der Veen, Renske M. and Kas, Joshua J. and Milne, Christopher J. and Nahhas, Amal El and Lima, Frederico A. and Vithanage, Dimali A. and Rehr, John J. and Abela, Rafael and Chergui, Majed and Pham, Van-Thai},
  issn         = {1463-9076},
  language     = {eng},
  month        = {01},
  number       = {21},
  pages        = {5551--5561},
  publisher    = {Royal Society of Chemistry},
  series       = {Physical Chemistry Chemical Physics},
  title        = {L-edge XANES analysis of photoexcited metal complexes in solution},
  url          = {http://dx.doi.org/10.1039/b927033g},
  volume       = {12},
  year         = {2010},
}