Observing Solvation Dynamics with Simultaneous Femtosecond X-ray Emission Spectroscopy and X-ray Scattering

Kristoffer Haldrup, Wojciech Gawelda, Rafael Abela, Roberto Alonso-Mori, Uwe Bergmann, Amelie Bordage, Marco Cammarata, Sophie E. Canton, Asmus Ougaard Dohn, Tim Brandt van Driel, David M. Fritz, Andreas Galler, Pieter Glatzel, Tobias Harlang, Kasper Skov Kjær, Henrik T. Lemke, Klaus Braagaard Møller, Zoltan Nemeth, Mátyás Imre Pápai, Norbert Sas & 6 others Jens Uhlig, Diling Zhu, György Vanko, Villy Sundström, Martin Meedom Nielsen, Christian Bressler

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

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.
Original languageEnglish
JournalJournal of physical chemistry b
Volume120
Issue number6
Pages (from-to)1158-1168
Number of pages11
ISSN1520-6106
DOIs
Publication statusPublished - 2016

Cite this

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. / Observing Solvation Dynamics with Simultaneous Femtosecond X-ray Emission Spectroscopy and X-ray Scattering. In: Journal of physical chemistry b. 2016 ; Vol. 120, No. 6. pp. 1158-1168.
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title = "Observing Solvation Dynamics with Simultaneous Femtosecond X-ray Emission Spectroscopy and X-ray Scattering",
abstract = "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.",
author = "Kristoffer Haldrup and Wojciech Gawelda and Rafael Abela and Roberto Alonso-Mori and Uwe Bergmann and Amelie Bordage and Marco Cammarata and Canton, {Sophie E.} and Dohn, {Asmus Ougaard} and {Brandt van Driel}, Tim and Fritz, {David M.} and Andreas Galler and Pieter Glatzel and Tobias Harlang and Kj{\ae}r, {Kasper Skov} and Lemke, {Henrik T.} and M{\o}ller, {Klaus Braagaard} and Zoltan Nemeth and P{\'a}pai, {M{\'a}ty{\'a}s Imre} and Norbert Sas and Jens Uhlig and Diling Zhu and Gy{\"o}rgy Vanko and Villy Sundstr{\"o}m and Nielsen, {Martin Meedom} and Christian Bressler",
year = "2016",
doi = "10.1021/acs.jpcb.5b12471",
language = "English",
volume = "120",
pages = "1158--1168",
journal = "Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical",
issn = "1520-6106",
publisher = "American Chemical Society",
number = "6",

}

Haldrup, K, Gawelda, W, Abela, R, Alonso-Mori, R, Bergmann, U, Bordage, A, Cammarata, M, Canton, SE, Dohn, AO, Brandt van Driel, T, Fritz, DM, Galler, A, Glatzel, P, Harlang, T, Kjær, KS, Lemke, HT, Møller, KB, Nemeth, Z, Pápai, MI, Sas, N, Uhlig, J, Zhu, D, Vanko, G, Sundström, V, Nielsen, MM & Bressler, C 2016, 'Observing Solvation Dynamics with Simultaneous Femtosecond X-ray Emission Spectroscopy and X-ray Scattering', Journal of physical chemistry b, vol. 120, no. 6, pp. 1158-1168. https://doi.org/10.1021/acs.jpcb.5b12471

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 journalJournal articleResearchpeer-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 -