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  Detailed Characterization of a Nanosecond-Lived Excited State: X-ray and Theoretical Investigation of the Quintet State in Photoexcited [Fe(terpy)2]2+

Vankó, G., Bordage, A., Pápai, M., Haldrup, K., Glatzel, P., March, A. M., et al. (2015). Detailed Characterization of a Nanosecond-Lived Excited State: X-ray and Theoretical Investigation of the Quintet State in Photoexcited [Fe(terpy)2]2+. The Journal of Physical Chemistry C, 119(11), 5888-5902. doi:10.1021/acs.jpcc.5b00557.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-002A-603B-2 Version Permalink: http://hdl.handle.net/11858/00-001M-0000-002A-603C-F
Genre: Journal Article

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© G. Vankó et al.

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http://dx.doi.org/10.1021/acs.jpcc.5b00557 (Publisher version)
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 Creators:
Vankó, György1, Author
Bordage, Amélie1, Author
Pápai, Mátyás1, Author
Haldrup, Kristoffer2, Author
Glatzel, Pieter3, Author
March, Anne Marie4, Author
Doumy, Gilles4, Author
Britz, Alexander5, 6, 7, Author              
Galler, Andreas5, Author
Assefa, Tadesse5, Author
Cabaret, Delphine8, Author
Juhin, Amélie8, Author
van Driel, Tim B.2, Author
Kjær, Kasper S.2, 9, Author
Dohn, Asmus10, Author
Møller, Klaus B.10, Author
Lemke, Henrik T.11, Author
Gallo, Erik3, Author
Rovezzi, Mauro3, Author
Németh, Zoltán1, Author
Rozsályi, Emese1, AuthorRozgonyi, Tamás12, AuthorUhlig, Jens9, AuthorSundström, Villy9, AuthorNielsen, Martin M.2, AuthorYoung, Linda4, AuthorSouthworth, Stephen H.4, AuthorBressler, Christian5, 7, AuthorGawelda, Wojciech5, Author more..
Affiliations:
1Wigner Research Centre for Physics, Hungarian Academy Sciences, P.O.B. 49., H-1525 Budapest, Hungary, ou_persistent22              
2Centre for Molecular Movies, Technical University of Denmark, Department of Physics, DK-2800 Kgs. Lyngby, Denmark, ou_persistent22              
3European Synchrotron Radiation Facility (ESRF), CS40220, Grenoble 38043 Cedex 9, France, ou_persistent22              
4X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States, ou_persistent22              
5European XFEL, Albert-Einstein-Ring 19, D-22761 Hamburg, Germany, ou_persistent22              
6International Max Planck Research School for Ultrafast Imaging & Structural Dynamics (IMPRS-UFAST), Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society, ou_2266714              
7The Hamburg Centre for Ultrafast Imaging, Luruper Chaussee 149, 22761 Hamburg, Germany, ou_persistent22              
8Institut de Minéralogie, de Physique des Matériaux, et de Cosmochimie (IMPMC), Sorbonne Universités - UPMC Univ. Paris 06, UMR CNRS 7590, Muséum National d’Histoire Naturelle, UR IRD 206, 4 Place Jussieu, F-75005 Paris, France, ou_persistent22              
9Department of Chemical Physics, Lund University, Box 124, 22100 Lund, Sweden, ou_persistent22              
10Centre for Molecular Movies, Technical University of Denmark, Department of Chemistry, DK-2800 Kgs. Lyngby, Denmark, ou_persistent22              
11SLAC National Accelerator Laboratory, Linac Coherent Light Source, Menlo Park, California 94025, United States, ou_persistent22              
12Research Centre for Natural Sciences, Hungarian Academy of Sciences, P.O. Box 286, H-1519 Budapest, Hungary, ou_persistent22              

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 Abstract: Theoretical predictions show that depending on the populations of the Fe 3dxy, 3dxz, and 3dyz orbitals two possible quintet states can exist for the high-spin state of the photoswitchable model system [Fe(terpy)2]2+. The differences in the structure and molecular properties of these 5B2 and 5E quintets are very small and pose a substantial challenge for experiments to resolve them. Yet for a better understanding of the physics of this system, which can lead to the design of novel molecules with enhanced photoswitching performance, it is vital to determine which high-spin state is reached in the transitions that follow the light excitation. The quintet state can be prepared with a short laser pulse and can be studied with cutting-edge time-resolved X-ray techniques. Here we report on the application of an extended set of X-ray spectroscopy and scattering techniques applied to investigate the quintet state of [Fe(terpy)2]2+ 80 ps after light excitation. High-quality X-ray absorption, nonresonant emission, and resonant emission spectra as well as X-ray diffuse scattering data clearly reflect the formation of the high-spin state of the [Fe(terpy)2]2+ molecule; moreover, extended X-ray absorption fine structure spectroscopy resolves the Fe–ligand bond-length variations with unprecedented bond-length accuracy in time-resolved experiments. With ab initio calculations we determine why, in contrast to most related systems, one configurational mode is insufficient for the description of the low-spin (LS)–high-spin (HS) transition. We identify the electronic structure origin of the differences between the two possible quintet modes, and finally, we unambiguously identify the formed quintet state as 5E, in agreement with our theoretical expectations.

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Language(s): eng - English
 Dates: 2015-02-242015-01-192015-02-252015-03-19
 Publication Status: Published in print
 Pages: 15
 Publishing info: -
 Table of Contents: -
 Rev. Method: Peer
 Identifiers: DOI: 10.1021/acs.jpcc.5b00557
 Degree: -

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Title: The Journal of Physical Chemistry C
  Abbreviation : J. Phys. Chem. C
Source Genre: Journal
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Publ. Info: Washington DC : American Chemical Society
Pages: - Volume / Issue: 119 (11) Sequence Number: - Start / End Page: 5888 - 5902 Identifier: ISSN: 1932-7447
CoNE: /journals/resource/954926947766