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Ring-Closing Reaction in Diarylethene Captured by Femtosecond Electron Crystallography

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Jean-Ruel,  Hubert
Departments of Chemistry and Physics, University of Toronto;
Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;

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Gao,  Meng
Departments of Chemistry and Physics, University of Toronto;
Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;

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Liu,  Lai Chung
Departments of Chemistry and Physics, University of Toronto;
Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;

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Miller,  R. J. Dwayne
Departments of Chemistry and Physics, University of Toronto;
Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;

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Citation

Jean-Ruel, H., Gao, M., Kochman, M. A., Lu, C., Liu, L. C., Cooney, R. R., et al. (2013). Ring-Closing Reaction in Diarylethene Captured by Femtosecond Electron Crystallography. The Journal of Physical Chemistry B, 117(49), 15894-15902. doi:10.1021/jp409245h.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0019-8F43-F
Abstract
The photoinduced ring-closing reaction in diarylethene, which serves as a model system for understanding reactive crossings through conical intersections, was directly observed with atomic resolution using femtosecond electron diffraction. Complementary ab initio calculations were also performed. Immediately following photoexcitation, subpicosecond structural changes associated with the formation of an open-ring excited-state intermediate were resolved. The key motion is the rotation of the thiophene rings, which significantly decreases the distance between the reactive carbon atoms prior to ring closing. Subsequently, on the few picosecond time scale, localized torsional motions of the carbon atoms lead to the formation of the closed-ring photoproduct. These direct observations of the molecular motions driving an organic chemical reaction were only made possible through the development of an ultrabright electron source to capture the atomic motions within the limited number of sampling frames and the low data acquisition rate dictated by the intrinsically poor thermal conductivity and limited photoreversibility of organic materials.