Coherent structural trapping through wave packet dispersion during photoinduced spin state switching
(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.
(Less)
- author
- organization
- publishing date
- 2017-05-24
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Nature Communications
- volume
- 8
- article number
- 15342
- publisher
- Nature Publishing Group
- external identifiers
-
- pmid:28537270
- wos:000401959300001
- scopus:85019918409
- ISSN
- 2041-1723
- DOI
- 10.1038/ncomms15342
- language
- English
- LU publication?
- yes
- id
- 190cbf43-c7b6-481b-900d-5977b9283517
- date added to LUP
- 2017-06-14 13:06:01
- date last changed
- 2025-02-04 20:38:04
@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>}},
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}},
doi = {{10.1038/ncomms15342}},
volume = {{8}},
year = {{2017}},
}