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Coherent structural trapping through wave packet dispersion during photoinduced spin state switching

Lemke, Henrik T.; Kjær, Kasper S. LU ; Hartsock, Robert W.; van Driel, Tim B; Chollet, Matthieu; Glownia, James M.; Song, Sanghoon; Zhu, Diling; Pace, Elisabetta and Matar, Samir F., et al. (2017) In Nature Communications 8.
Abstract

The description of ultrafast nonadiabatic chemical dynamics during molecular photo-transformations remains challenging because electronic and nuclear configurations impact each other and cannot be treated independently. Here we gain experimental insights, beyond the Born-Oppenheimer approximation, into the light-induced spin-state trapping dynamics of the prototypical [Fe(bpy) 3 ] 2+ compound by time-resolved X-ray absorption spectroscopy at sub-30-femtosecond resolution and high signal-to-noise ratio. The electronic decay from the initial optically excited electronic state towards the high spin state is distinguished from the structural trapping dynamics, which launches a coherent oscillating wave packet (265 fs period), clearly... (More)

The description of ultrafast nonadiabatic chemical dynamics during molecular photo-transformations remains challenging because electronic and nuclear configurations impact each other and cannot be treated independently. Here we gain experimental insights, beyond the Born-Oppenheimer approximation, into the light-induced spin-state trapping dynamics of the prototypical [Fe(bpy) 3 ] 2+ compound by time-resolved X-ray absorption spectroscopy at sub-30-femtosecond resolution and high signal-to-noise ratio. The electronic decay from the initial optically excited electronic state towards the high spin state is distinguished from the structural trapping dynamics, which launches a coherent oscillating wave packet (265 fs period), clearly identified as molecular breathing. Throughout the structural trapping, the dispersion of the wave packet along the reaction coordinate reveals details of intramolecular vibronic coupling before a slower vibrational energy dissipation to the solution environment. These findings illustrate how modern time-resolved X-ray absorption spectroscopy can provide key information to unravel dynamic details of photo-functional molecules.

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Nature Communications
volume
8
publisher
Nature Publishing Group
external identifiers
  • scopus:85019918409
  • wos:000401959300001
ISSN
2041-1723
DOI
10.1038/ncomms15342
language
English
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yes
id
190cbf43-c7b6-481b-900d-5977b9283517
date added to LUP
2017-06-14 13:06:01
date last changed
2017-09-18 11:41:07
@article{190cbf43-c7b6-481b-900d-5977b9283517,
  abstract     = {<p>The description of ultrafast nonadiabatic chemical dynamics during molecular photo-transformations remains challenging because electronic and nuclear configurations impact each other and cannot be treated independently. Here we gain experimental insights, beyond the Born-Oppenheimer approximation, into the light-induced spin-state trapping dynamics of the prototypical [Fe(bpy) 3 ] 2+ compound by time-resolved X-ray absorption spectroscopy at sub-30-femtosecond resolution and high signal-to-noise ratio. The electronic decay from the initial optically excited electronic state towards the high spin state is distinguished from the structural trapping dynamics, which launches a coherent oscillating wave packet (265 fs period), clearly identified as molecular breathing. Throughout the structural trapping, the dispersion of the wave packet along the reaction coordinate reveals details of intramolecular vibronic coupling before a slower vibrational energy dissipation to the solution environment. These findings illustrate how modern time-resolved X-ray absorption spectroscopy can provide key information to unravel dynamic details of photo-functional molecules.</p>},
  articleno    = {15342},
  author       = {Lemke, Henrik T. and Kjær, Kasper S. and Hartsock, Robert W. and van Driel, Tim B and Chollet, Matthieu and Glownia, James M. and Song, Sanghoon and Zhu, Diling and Pace, Elisabetta and Matar, Samir F. and Nielsen, Martin M. and Benfatto, Maurizio and Gaffney, Kelly J. and Collet, Eric and Cammarata, Marco},
  issn         = {2041-1723},
  language     = {eng},
  month        = {05},
  publisher    = {Nature Publishing Group},
  series       = {Nature Communications},
  title        = {Coherent structural trapping through wave packet dispersion during photoinduced spin state switching},
  url          = {http://dx.doi.org/10.1038/ncomms15342},
  volume       = {8},
  year         = {2017},
}