Abstract
| Original language | English |
|---|---|
| Journal | Journal of physical chemistry b |
| Volume | 120 |
| Issue number | 6 |
| Pages (from-to) | 1158-1168 |
| Number of pages | 11 |
| ISSN | 1520-6106 |
| DOIs | |
| Publication status | Published - 2016 |
Cite this
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Observing Solvation Dynamics with Simultaneous Femtosecond X-ray Emission Spectroscopy and X-ray Scattering. / Haldrup, Kristoffer; Gawelda, Wojciech; Abela, Rafael; Alonso-Mori, Roberto; Bergmann, Uwe; Bordage, Amelie; Cammarata, Marco; Canton, Sophie E.; Dohn, Asmus Ougaard; Brandt van Driel, Tim; Fritz, David M.; Galler, Andreas; Glatzel, Pieter; Harlang, Tobias ; Kjær, Kasper Skov; Lemke, Henrik T.; Møller, Klaus Braagaard; Nemeth, Zoltan; Pápai, Mátyás Imre; Sas, Norbert; Uhlig, Jens; Zhu, Diling; Vanko, György; Sundström, Villy; Nielsen, Martin Meedom; Bressler, Christian.
In: Journal of physical chemistry b, Vol. 120, No. 6, 2016, p. 1158-1168.Research output: Contribution to journal › Journal article › Research › peer-review
TY - JOUR
T1 - Observing Solvation Dynamics with Simultaneous Femtosecond X-ray Emission Spectroscopy and X-ray Scattering
AU - Haldrup, Kristoffer
AU - Gawelda, Wojciech
AU - Abela, Rafael
AU - Alonso-Mori, Roberto
AU - Bergmann, Uwe
AU - Bordage, Amelie
AU - Cammarata, Marco
AU - Canton, Sophie E.
AU - Dohn, Asmus Ougaard
AU - Brandt van Driel, Tim
AU - Fritz, David M.
AU - Galler, Andreas
AU - Glatzel, Pieter
AU - Harlang, Tobias
AU - Kjær, Kasper Skov
AU - Lemke, Henrik T.
AU - Møller, Klaus Braagaard
AU - Nemeth, Zoltan
AU - Pápai, Mátyás Imre
AU - Sas, Norbert
AU - Uhlig, Jens
AU - Zhu, Diling
AU - Vanko, György
AU - Sundström, Villy
AU - Nielsen, Martin Meedom
AU - Bressler, Christian
PY - 2016
Y1 - 2016
N2 - In liquid phase chemistry dynamic solute solvent interactions often govern the path, ultimate outcome, and efficiency of chemical reactions. These steps involve many-body movements on subpicosecond time scales and thus ultrafast structural tools capable of capturing both intramolecular electronic and structural changes, and local solvent structural changes are desired. We have studied the intra- and intermolecular dynamics of a model chromophore, aqueous [Fe(bpy)3]2+, with complementary X-ray tools in a single experiment exploiting intense XFEL radiation as a probe. We monitored the ultrafast structural rearrangement of the solute with X-ray emission spectroscopy, thus establishing time zero for the ensuing X-ray diffuse scattering analysis. The simultaneously recorded X-ray diffuse scattering atterns reveal slower subpicosecond dynamics triggered by the intramolecular structural dynamics of the photoexcited solute. By simultaneous combination of both methods only, we can extract new information about the solvation dynamic processes unfolding during the first picosecond (ps). The measured bulk solvent density increase of 0.2% indicates a dramatic change of the solvation shell around each photoexcited solute, confirming previous ab initio molecular dynamics simulations. Structural changes in the aqueous solvent associated with density and temperature changes occur with similar to 1 ps time constants, characteristic for structural dynamics in water. This slower time scale of the solvent response allows us to directly observe the structure of the excited solute molecules well before the solvent contributions become dominant.
AB - In liquid phase chemistry dynamic solute solvent interactions often govern the path, ultimate outcome, and efficiency of chemical reactions. These steps involve many-body movements on subpicosecond time scales and thus ultrafast structural tools capable of capturing both intramolecular electronic and structural changes, and local solvent structural changes are desired. We have studied the intra- and intermolecular dynamics of a model chromophore, aqueous [Fe(bpy)3]2+, with complementary X-ray tools in a single experiment exploiting intense XFEL radiation as a probe. We monitored the ultrafast structural rearrangement of the solute with X-ray emission spectroscopy, thus establishing time zero for the ensuing X-ray diffuse scattering analysis. The simultaneously recorded X-ray diffuse scattering atterns reveal slower subpicosecond dynamics triggered by the intramolecular structural dynamics of the photoexcited solute. By simultaneous combination of both methods only, we can extract new information about the solvation dynamic processes unfolding during the first picosecond (ps). The measured bulk solvent density increase of 0.2% indicates a dramatic change of the solvation shell around each photoexcited solute, confirming previous ab initio molecular dynamics simulations. Structural changes in the aqueous solvent associated with density and temperature changes occur with similar to 1 ps time constants, characteristic for structural dynamics in water. This slower time scale of the solvent response allows us to directly observe the structure of the excited solute molecules well before the solvent contributions become dominant.
U2 - 10.1021/acs.jpcb.5b12471
DO - 10.1021/acs.jpcb.5b12471
M3 - Journal article
VL - 120
SP - 1158
EP - 1168
JO - Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical
JF - Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical
SN - 1520-6106
IS - 6
ER -