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

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 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.

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [3];  [3]; ORCiD logo [3];  [3]; ORCiD logo [5];  [6]; ORCiD logo [7];  [5];  [3]; ORCiD logo [8]; ORCiD logo [8]
  1. SLAC National Accelerator Lab., Menlo Park, CA (United States); Paul Scherrer Inst. (PSI), Villigen (Switzerland)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States); Technical Univ. of Denmark, Lyngby (Denmark); Lund Univ. (Sweden)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States); Technical Univ. of Denmark, Lyngby (Denmark)
  5. Istituto Nazionale di Fisica Nucleare (INFN), Frascati (Italy)
  6. Univ. of Bordeaux (France)
  7. Technical Univ. of Denmark, Lyngby (Denmark)
  8. Univ. of Rennes (France)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1367851
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Lemke, Henrik T., Kjær, Kasper S., Hartsock, Robert, van Driel, Tim B., Chollet, Matthieu, Glownia, James M., Song, Sanghoon, Zhu, Diling, Pace, Elisabetta, Matar, Samir F., Nielsen, Martin M., Benfatto, Maurizio, Gaffney, Kelly J., Collet, Eric, and Cammarata, Marco. Coherent structural trapping through wave packet dispersion during photoinduced spin state switching. United States: N. p., 2017. Web. doi:10.1038/ncomms15342.
Lemke, Henrik T., Kjær, Kasper S., Hartsock, Robert, van Driel, Tim B., Chollet, Matthieu, Glownia, James M., Song, Sanghoon, Zhu, Diling, Pace, Elisabetta, Matar, Samir F., Nielsen, Martin M., Benfatto, Maurizio, Gaffney, Kelly J., Collet, Eric, & Cammarata, Marco. Coherent structural trapping through wave packet dispersion during photoinduced spin state switching. United States. doi:10.1038/ncomms15342.
Lemke, Henrik T., Kjær, Kasper S., Hartsock, Robert, van Driel, Tim B., Chollet, Matthieu, Glownia, James M., Song, Sanghoon, Zhu, Diling, Pace, Elisabetta, Matar, Samir F., Nielsen, Martin M., Benfatto, Maurizio, Gaffney, Kelly J., Collet, Eric, and Cammarata, Marco. Wed . "Coherent structural trapping through wave packet dispersion during photoinduced spin state switching". United States. doi:10.1038/ncomms15342. https://www.osti.gov/servlets/purl/1367851.
@article{osti_1367851,
title = {Coherent structural trapping through wave packet dispersion during photoinduced spin state switching},
author = {Lemke, Henrik T. and Kjær, Kasper S. and Hartsock, Robert 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},
abstractNote = {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.},
doi = {10.1038/ncomms15342},
journal = {Nature Communications},
number = ,
volume = 8,
place = {United States},
year = {2017},
month = {5}
}

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