Ultrafast time-resolved wide angle x-ray scattering from chemical reactions in solution has recently emerged as a powerful technique for determining the structural dynamics of transient photochemical species. Here we examine the structural evolution of photoexcited in the nonpolar solvent cyclohexane and draw comparisons with a similar study in the polar solvent methanol. As with earlier spectroscopic studies, our data confirm a common initial reaction pathway in both solvents. After photoexcitation, dissociates to form . Iodine radicals remaining within the solvent cage recombine with a nascent radical to form the transient isomer , whereas those which escape the solvent cage ultimately combine to form in cyclohexane. Moreover, the transient isomer has a lifetime approximately 30 times longer in the nonpolar solvent. Of greater chemical significance is the property of time-resolved wide angle x-ray diffraction to accurately determine the structure of the of reaction intermediate. Thus we observe that the transient iodine-iodine bond is shorter in cyclohexane than in methanol. A longer iodine-iodine bond length for the intermediate arises in methanol due to favorable H-bond interaction with the polar solvent. These findings establish that time-resolved x-ray diffraction has sufficient sensitivity to enable solvent dependent structural perturbations of transient chemical species to be accurately resolved.
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21 April 2009
Research Article|
April 15 2009
Solvent dependent structural perturbations of chemical reaction intermediates visualized by time-resolved x-ray diffraction
Jonathan Vincent;
Jonathan Vincent
1Department of Photochemistry and Molecular Science,
Uppsala University
, P.O. Box 523, S-751 20 Uppsala, Sweden
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Magnus Andersson;
Magnus Andersson
2Department of Chemical and Biological Engineering,
Chalmers University of Technology
, P.O. Box 462, S-405 30 Gothenburg, Sweden
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Mattias Eklund;
Mattias Eklund
1Department of Photochemistry and Molecular Science,
Uppsala University
, P.O. Box 523, S-751 20 Uppsala, Sweden
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Annemarie B. Wöhri;
Annemarie B. Wöhri
2Department of Chemical and Biological Engineering,
Chalmers University of Technology
, P.O. Box 462, S-405 30 Gothenburg, Sweden
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Michael Odelius;
Michael Odelius
3FYSIKUM,
Stockholm University
, Albanova, S-106 91 Stockholm, Sweden
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Erik Malmerberg;
Erik Malmerberg
4Department of Chemistry, Biochemistry and Biophysics,
Gothenburg University
, P.O. Box 462, S-405 30 Gothenburg, Sweden
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Qingyu Kong;
Qingyu Kong
5
European Synchrotron Radiation Facility
, BP 220, F-38043 Grenoble, France
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Michael Wulff;
Michael Wulff
5
European Synchrotron Radiation Facility
, BP 220, F-38043 Grenoble, France
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Richard Neutze;
Richard Neutze
4Department of Chemistry, Biochemistry and Biophysics,
Gothenburg University
, P.O. Box 462, S-405 30 Gothenburg, Sweden
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Jan Davidsson
Jan Davidsson
a)
1Department of Photochemistry and Molecular Science,
Uppsala University
, P.O. Box 523, S-751 20 Uppsala, Sweden
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Jonathan Vincent
1
Magnus Andersson
2
Mattias Eklund
1
Annemarie B. Wöhri
2
Michael Odelius
3
Erik Malmerberg
4
Qingyu Kong
5
Michael Wulff
5
Richard Neutze
4
Jan Davidsson
1,a)
1Department of Photochemistry and Molecular Science,
Uppsala University
, P.O. Box 523, S-751 20 Uppsala, Sweden
2Department of Chemical and Biological Engineering,
Chalmers University of Technology
, P.O. Box 462, S-405 30 Gothenburg, Sweden
3FYSIKUM,
Stockholm University
, Albanova, S-106 91 Stockholm, Sweden
4Department of Chemistry, Biochemistry and Biophysics,
Gothenburg University
, P.O. Box 462, S-405 30 Gothenburg, Sweden
5
European Synchrotron Radiation Facility
, BP 220, F-38043 Grenoble, France
a)
Electronic mail: [email protected].
J. Chem. Phys. 130, 154502 (2009)
Article history
Received:
February 16 2009
Accepted:
February 22 2009
Citation
Jonathan Vincent, Magnus Andersson, Mattias Eklund, Annemarie B. Wöhri, Michael Odelius, Erik Malmerberg, Qingyu Kong, Michael Wulff, Richard Neutze, Jan Davidsson; Solvent dependent structural perturbations of chemical reaction intermediates visualized by time-resolved x-ray diffraction. J. Chem. Phys. 21 April 2009; 130 (15): 154502. https://doi.org/10.1063/1.3111401
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