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+)
(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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- organization
- publishing date
- 2012
- type
- Contribution to journal
- publication status
- published
- subject
- in
- 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 (ACS)
- external identifiers
-
- wos:000309648800011
- scopus:84868152480
- pmid:22970732
- ISSN
- 1520-5215
- DOI
- 10.1021/jp306917x
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Chemical Physics (S) (011001060)
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- f1d51f7f-4531-400b-b6ca-4d6217954644 (old id 3181359)
- date added to LUP
- 2016-04-01 14:15:31
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- 2022-04-14 08:53:16
@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 (ACS)}},
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}},
doi = {{10.1021/jp306917x}},
volume = {{116}},
year = {{2012}},
}