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Guest-Host Interactions Investigated by Time-Resolved X-ray Spectroscopies and Scattering at MHz Rates: Solvation Dynamics and Photoinduced Spin Transition in Aqueous Fe(bipy)(3)(2+)

Haldrup, K.; Vanko, G.; Gawelda, W.; Galler, A.; Doumy, G.; March, A. M.; Kanter, E. P.; Bordage, A.; Dohn, A. and van Driel, T. B., et al. (2012) In The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 116(40). p.9878-9887
Abstract
We have studied the photoinduced low spin (LS) to high spin (HS) conversion of [Fe(bipy)(3)](2+) in aqueous solution. In a laser pump/X-ray probe synchrotron setup permitting simultaneous, time-resolved X-ray diffuse scattering (XDS) and X-ray spectroscopic measurements at a 3.26 MHz repetition rate, we observed the interplay between intramolecular dynamics and the intermolecular caging solvent response with better than 100 ps time resolution. On this time scale, the initial ultrafast spin transition and the associated intramolecular geometric structure changes are long completed, as is the solvent heating due to the initial energy dissipation from the excited HS molecule. Combining information from X-ray emission spectroscopy and... (More)
We have studied the photoinduced low spin (LS) to high spin (HS) conversion of [Fe(bipy)(3)](2+) in aqueous solution. In a laser pump/X-ray probe synchrotron setup permitting simultaneous, time-resolved X-ray diffuse scattering (XDS) and X-ray spectroscopic measurements at a 3.26 MHz repetition rate, we observed the interplay between intramolecular dynamics and the intermolecular caging solvent response with better than 100 ps time resolution. On this time scale, the initial ultrafast spin transition and the associated intramolecular geometric structure changes are long completed, as is the solvent heating due to the initial energy dissipation from the excited HS molecule. Combining information from X-ray emission spectroscopy and scattering, the excitation fraction as well as the temperature and density changes of the solvent can be closely followed on the subnanosecond time scale of the HS lifetime, allowing the detection of an ultrafast change in bulk solvent density. An analysis approach directly utilizing the spectroscopic data in the XDS analysis effectively reduces the number of free parameters, and both combined permit extraction of information about the ultrafast structural dynamics of the caging solvent, in particular, a decrease in the number of water molecules in the first solvation shell is inferred, as predicted by recent theoretical work. (Less)
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published
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The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
volume
116
issue
40
pages
9878 - 9887
publisher
The American Chemical Society
external identifiers
  • wos:000309648800011
  • scopus:84868152480
ISSN
1520-5215
DOI
10.1021/jp306917x
language
English
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yes
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f1d51f7f-4531-400b-b6ca-4d6217954644 (old id 3181359)
date added to LUP
2012-12-06 14:55:00
date last changed
2017-11-19 03:54:47
@article{f1d51f7f-4531-400b-b6ca-4d6217954644,
  abstract     = {We have studied the photoinduced low spin (LS) to high spin (HS) conversion of [Fe(bipy)(3)](2+) in aqueous solution. In a laser pump/X-ray probe synchrotron setup permitting simultaneous, time-resolved X-ray diffuse scattering (XDS) and X-ray spectroscopic measurements at a 3.26 MHz repetition rate, we observed the interplay between intramolecular dynamics and the intermolecular caging solvent response with better than 100 ps time resolution. On this time scale, the initial ultrafast spin transition and the associated intramolecular geometric structure changes are long completed, as is the solvent heating due to the initial energy dissipation from the excited HS molecule. Combining information from X-ray emission spectroscopy and scattering, the excitation fraction as well as the temperature and density changes of the solvent can be closely followed on the subnanosecond time scale of the HS lifetime, allowing the detection of an ultrafast change in bulk solvent density. An analysis approach directly utilizing the spectroscopic data in the XDS analysis effectively reduces the number of free parameters, and both combined permit extraction of information about the ultrafast structural dynamics of the caging solvent, in particular, a decrease in the number of water molecules in the first solvation shell is inferred, as predicted by recent theoretical work.},
  author       = {Haldrup, K. and Vanko, G. and Gawelda, W. and Galler, A. and Doumy, G. and March, A. M. and Kanter, E. P. and Bordage, A. and Dohn, A. and van Driel, T. B. and Kjaer, K. S. and Lemke, H. T. and Canton, Sophie and Uhlig, J. and Sundström, Villy and Young, L. and Southworth, S. H. and Nielsen, M. M. and Bressler, C.},
  issn         = {1520-5215},
  language     = {eng},
  number       = {40},
  pages        = {9878--9887},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory},
  title        = {Guest-Host Interactions Investigated by Time-Resolved X-ray Spectroscopies and Scattering at MHz Rates: Solvation Dynamics and Photoinduced Spin Transition in Aqueous Fe(bipy)(3)(2+)},
  url          = {http://dx.doi.org/10.1021/jp306917x},
  volume       = {116},
  year         = {2012},
}