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Solvation dynamics monitored by combined X-ray spectroscopies and scattering: photoinduced spin transition in aqueous [Fe(bpy)(3)](2+)

Bressler, C.; Gawelda, W.; Galler, A.; Nielsen, M. M.; Sundström, Villy LU ; Doumy, G.; March, A. M.; Southworth, S. H.; Young, L. and Vanko, G. (2014) In Faraday Discussions 171. p.169-178
Abstract
We have studied the photoinduced low spin (LS) to high spin (HS) conversion of aqueous Fe(bpy)(3) with pulse-limited time resolution. In a combined setup permitting simultaneous X-ray diffuse scattering (XDS) and spectroscopic measurements at a MHz repetition rate we have unraveled the interplay between intramolecular dynamics and the intermolecular caging solvent response with 100 ps time resolution. On this time scale the ultrafast spin transition including intramolecular geometric structure changes as well as the concomitant bulk solvent heating process due to energy dissipation from the excited HS molecule are long completed. The heating is nevertheless observed to further increase due to the excess energy between HS and LS states... (More)
We have studied the photoinduced low spin (LS) to high spin (HS) conversion of aqueous Fe(bpy)(3) with pulse-limited time resolution. In a combined setup permitting simultaneous X-ray diffuse scattering (XDS) and spectroscopic measurements at a MHz repetition rate we have unraveled the interplay between intramolecular dynamics and the intermolecular caging solvent response with 100 ps time resolution. On this time scale the ultrafast spin transition including intramolecular geometric structure changes as well as the concomitant bulk solvent heating process due to energy dissipation from the excited HS molecule are long completed. The heating is nevertheless observed to further increase due to the excess energy between HS and LS states released on a subnanosecond time scale. The analysis of the spectroscopic data allows precise determination of the excited population which efficiently reduces the number of free parameters in the XDS analysis, and both combined permit extraction of information about the structural dynamics of the first solvation shell. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Faraday Discussions
volume
171
pages
169 - 178
publisher
Royal Society of Chemistry
external identifiers
  • wos:000345529900009
  • scopus:84912028922
ISSN
1364-5498
DOI
10.1039/c4fd00097h
language
English
LU publication?
yes
id
2ac1d3ba-48ad-4461-b507-114be7c6c4ac (old id 4982631)
date added to LUP
2015-01-27 12:01:42
date last changed
2017-09-03 03:18:14
@article{2ac1d3ba-48ad-4461-b507-114be7c6c4ac,
  abstract     = {We have studied the photoinduced low spin (LS) to high spin (HS) conversion of aqueous Fe(bpy)(3) with pulse-limited time resolution. In a combined setup permitting simultaneous X-ray diffuse scattering (XDS) and spectroscopic measurements at a MHz repetition rate we have unraveled the interplay between intramolecular dynamics and the intermolecular caging solvent response with 100 ps time resolution. On this time scale the ultrafast spin transition including intramolecular geometric structure changes as well as the concomitant bulk solvent heating process due to energy dissipation from the excited HS molecule are long completed. The heating is nevertheless observed to further increase due to the excess energy between HS and LS states released on a subnanosecond time scale. The analysis of the spectroscopic data allows precise determination of the excited population which efficiently reduces the number of free parameters in the XDS analysis, and both combined permit extraction of information about the structural dynamics of the first solvation shell.},
  author       = {Bressler, C. and Gawelda, W. and Galler, A. and Nielsen, M. M. and Sundström, Villy and Doumy, G. and March, A. M. and Southworth, S. H. and Young, L. and Vanko, G.},
  issn         = {1364-5498},
  language     = {eng},
  pages        = {169--178},
  publisher    = {Royal Society of Chemistry},
  series       = {Faraday Discussions},
  title        = {Solvation dynamics monitored by combined X-ray spectroscopies and scattering: photoinduced spin transition in aqueous [Fe(bpy)(3)](2+)},
  url          = {http://dx.doi.org/10.1039/c4fd00097h},
  volume       = {171},
  year         = {2014},
}