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Journal Article

Ultrafast ring-opening and solvent-dependent product relaxation of photochromic spironaphthopyran

MPS-Authors
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Bittmann,  S.
Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;
Center for Free Electron Laser Science;

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Dsouza,  R.
Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;
Department of Physics, University of Hamburg;

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Siddiqui,  K. M.
Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;

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Hayes,  S. A.
Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;

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Rossos,  A.
Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;

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Corthey,  G.
Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;
Instituto de Nanosistemas, Universidad Nacional de San Martin;

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Kochman,  M.
Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;
Department of Physics, Chemistry and Biology (IFM), Linköping University;

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Prokhorenko,  V.
Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;

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

External Resource

https://dx.doi.org/10.1039/c9cp02950h
(Publisher version)

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Fulltext (public)

c9cp02950h.pdf
(Publisher version), 6MB

Supplementary Material (public)

c9cp02950h1.pdf
(Supplementary material), 16MB

Citation

Bittmann, S., Dsouza, R., Siddiqui, K. M., Hayes, S. A., Rossos, A., Corthey, G., et al. (2019). Ultrafast ring-opening and solvent-dependent product relaxation of photochromic spironaphthopyran. Physical Chemistry Chemical Physics, 21(33), 18119-18127. doi:10.1039/c9cp02950h.


Cite as: https://hdl.handle.net/21.11116/0000-0004-A783-B
Abstract
The ultrafast dynamics of unsubstituted spironaphthopyran (SNP) were investigated using femtosecond transient UV and visible absorption spectroscopy in three different solvents and by semi-classical nuclear dynamics simulations. The primary ring-opening of the pyran unit was found to occur in 300 fs yielding a non-planar intermediate in the first singlet excited state (S1). Subsequent planarisation and relaxation to the product ground state proceed through barrier crossing on the S1 potential energy surface (PES) and take place within 1.1 ps after excitation. Simulations show that more than 90% of the trajectories involving C–O bond elongation lead to the planar, open-ring product, while relaxation back to the S0 of the closed-ring form is accompanied by C–N elongation. All ensuing spectral dynamics are ascribed to vibrational relaxation and thermalisation of the product with a time constant of 13 ps. The latter shows dependency on characteristics of the solvent with solvent relaxation kinetics playing a role.