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Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering

Kunnus, Kristjan ; Vacher, Morgane ; Harlang, Tobias C.B. LU ; Kjær, Kasper S. LU ; Haldrup, Kristoffer ; Biasin, Elisa ; van Driel, Tim B. ; Pápai, Mátyás ; Chabera, Pavel LU and Liu, Yizhu LU , et al. (2020) In Nature Communications 11.
Abstract

The non-equilibrium dynamics of electrons and nuclei govern the function of photoactive materials. Disentangling these dynamics remains a critical goal for understanding photoactive materials. Here we investigate the photoinduced dynamics of the [Fe(bmip)2]2+ photosensitizer, where bmip = 2,6-bis(3-methyl-imidazole-1-ylidine)-pyridine, with simultaneous femtosecond-resolution Fe Kα and Kβ X-ray emission spectroscopy (XES) and X-ray solution scattering (XSS). This measurement shows temporal oscillations in the XES and XSS difference signals with the same 278 fs period oscillation. These oscillations originate from an Fe-ligand stretching vibrational wavepacket on a triplet metal-centered (3MC) excited... (More)

The non-equilibrium dynamics of electrons and nuclei govern the function of photoactive materials. Disentangling these dynamics remains a critical goal for understanding photoactive materials. Here we investigate the photoinduced dynamics of the [Fe(bmip)2]2+ photosensitizer, where bmip = 2,6-bis(3-methyl-imidazole-1-ylidine)-pyridine, with simultaneous femtosecond-resolution Fe Kα and Kβ X-ray emission spectroscopy (XES) and X-ray solution scattering (XSS). This measurement shows temporal oscillations in the XES and XSS difference signals with the same 278 fs period oscillation. These oscillations originate from an Fe-ligand stretching vibrational wavepacket on a triplet metal-centered (3MC) excited state surface. This 3MC state is populated with a 110 fs time constant by 40% of the excited molecules while the rest relax to a 3MLCT excited state. The sensitivity of the Kα XES to molecular structure results from a 0.7% average Fe-ligand bond length shift between the 1 s and 2p core-ionized states surfaces.

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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Nature Communications
volume
11
article number
634
publisher
Nature Publishing Group
external identifiers
  • pmid:32005815
  • scopus:85078841027
ISSN
2041-1723
DOI
10.1038/s41467-020-14468-w
language
English
LU publication?
yes
id
1ecf1f3d-2ed2-48cc-9e30-6a91fa52a822
date added to LUP
2020-02-11 09:31:17
date last changed
2021-04-11 05:29:18
@article{1ecf1f3d-2ed2-48cc-9e30-6a91fa52a822,
  abstract     = {<p>The non-equilibrium dynamics of electrons and nuclei govern the function of photoactive materials. Disentangling these dynamics remains a critical goal for understanding photoactive materials. Here we investigate the photoinduced dynamics of the [Fe(bmip)<sub>2</sub>]<sup>2+</sup> photosensitizer, where bmip = 2,6-bis(3-methyl-imidazole-1-ylidine)-pyridine, with simultaneous femtosecond-resolution Fe Kα and Kβ X-ray emission spectroscopy (XES) and X-ray solution scattering (XSS). This measurement shows temporal oscillations in the XES and XSS difference signals with the same 278 fs period oscillation. These oscillations originate from an Fe-ligand stretching vibrational wavepacket on a triplet metal-centered (<sup>3</sup>MC) excited state surface. This <sup>3</sup>MC state is populated with a 110 fs time constant by 40% of the excited molecules while the rest relax to a <sup>3</sup>MLCT excited state. The sensitivity of the Kα XES to molecular structure results from a 0.7% average Fe-ligand bond length shift between the 1 s and 2p core-ionized states surfaces.</p>},
  author       = {Kunnus, Kristjan and Vacher, Morgane and Harlang, Tobias C.B. and Kjær, Kasper S. and Haldrup, Kristoffer and Biasin, Elisa and van Driel, Tim B. and Pápai, Mátyás and Chabera, Pavel and Liu, Yizhu and Tatsuno, Hideyuki and Timm, Cornelia and Källman, Erik and Delcey, Mickaël and Hartsock, Robert W. and Reinhard, Marco E. and Koroidov, Sergey and Laursen, Mads G. and Hansen, Frederik B. and Vester, Peter and Christensen, Morten and Sandberg, Lise and Németh, Zoltán and Szemes, Dorottya Sárosiné and Bajnóczi, Éva and Alonso-Mori, Roberto and Glownia, James M. and Nelson, Silke and Sikorski, Marcin and Sokaras, Dimosthenis and Lemke, Henrik T. and Canton, Sophie E. and Møller, Klaus B. and Nielsen, Martin M. and Vankó, György and Wärnmark, Kenneth and Sundström, Villy and Persson, Petter and Lundberg, Marcus and Uhlig, Jens and Gaffney, Kelly J.},
  issn         = {2041-1723},
  language     = {eng},
  month        = {01},
  publisher    = {Nature Publishing Group},
  series       = {Nature Communications},
  title        = {Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering},
  url          = {http://dx.doi.org/10.1038/s41467-020-14468-w},
  doi          = {10.1038/s41467-020-14468-w},
  volume       = {11},
  year         = {2020},
}