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Title: Femtosecond x-ray scattering study of ultrafast photoinduced structural dynamics in solvated [ Co ( terpy ) 2 ] 2 +

Abstract

Here, we study the structural dynamics of photoexcited [Co(terpy)2]2+ in an aqueous solution with ultrafast x-ray diffuse scattering experiments conducted at the Linac Coherent Light Source. Through direct comparisons with density functional theory calculations, our analysis shows that the photoexcitation event leads to elongation of the Co-N bonds, followed by coherent Co-N bond length oscillations arising from the impulsive excitation of a vibrational mode dominated by the symmetrical stretch of all six Co-N bonds. This mode has a period of 0.33 ps and decays on a subpicosecond time scale. We find that the equilibrium bond-elongated structure of the high spin state is established on a single-picosecond time scale and that this state has a lifetime of ~7 ps.

Authors:
 [1];  [1];  [2];  [1];  [1];  [3];  [3];  [3];  [3];  [4];  [5];  [6];  [6];  [7];  [6];  [6];  [6];  [6];  [6];  [8] more »;  [8];  [8];  [9];  [8];  [6];  [10];  [1];  [1];  [3];  [5];  [3];  [11];  [1] « less
  1. Technical Univ. of Denmark, Lyngby (Denmark)
  2. Technical Univ. of Denmark, Lyngby (Denmark); Lund Univ., Lund (Sweden); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. Lund Univ., Lund (Sweden)
  4. Technical Univ. of Denmark, Lyngby (Denmark): Hungarian Academy Sciences, Budapest (Hungary)
  5. Hungarian Academy Sciences, Budapest (Hungary)
  6. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  7. Tianjin Polytechnic Univ., Tianjin (China)
  8. European XFEL GmbH, Hamburg (Germany)
  9. European XFEL GmbH, Hamburg (Germany); Jan Kochanowski Univ., Kielce (Poland)
  10. SLAC National Accelerator Lab., Menlo Park, CA (United States); Paul Scherrer Inst. (PSI), Villigen (Switzerland)
  11. Max Planck Institute for Biophysical Chemistry, Goettingen (Germany); Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1335954
Alternate Identifier(s):
OSTI ID: 1259990
Grant/Contract Number:  
StG-259709; K29724; LP2013-59; 21302138; AC02-76SF00515; 20130504
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Letters
Additional Journal Information:
Journal Volume: 117; Journal Issue: 1; Journal ID: ISSN 0031-9007
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
43 PARTICLE ACCELERATORS

Citation Formats

Biasin, Elisa, van Driel, Tim Brandt, Kjær, Kasper S., Dohn, Asmus O., Christensen, Morten, Harlang, Tobias, Chabera, Pavel, Liu, Yizhu, Uhlig, Jens, Papai, Matyas, Nemeth, Zoltan, Hartsock, Robert, Liang, Winnie, Zhang, Jianxin, Alonso-Mori, Roberto, Chollet, Matthieu, Glownia, James M., Nelson, Silke, Sokaras, Dimosthenis, Assefa, Tadesse A., Britz, Alexander, Galler, Andreas, Gawelda, Wojciech, Bressler, Christian, Gaffney, Kelly J., Lemke, Henrik T., Moller, Klaus B., Nielsen, Martin M., Sundstrom, Villy, Vanko, Gyorgy, Warnmark, Kenneth, Canton, Sophie E., and Haldrup, Kristoffer. Femtosecond x-ray scattering study of ultrafast photoinduced structural dynamics in solvated [Co(terpy)2]2+. United States: N. p., 2016. Web. doi:10.1103/PhysRevLett.117.013002.
Biasin, Elisa, van Driel, Tim Brandt, Kjær, Kasper S., Dohn, Asmus O., Christensen, Morten, Harlang, Tobias, Chabera, Pavel, Liu, Yizhu, Uhlig, Jens, Papai, Matyas, Nemeth, Zoltan, Hartsock, Robert, Liang, Winnie, Zhang, Jianxin, Alonso-Mori, Roberto, Chollet, Matthieu, Glownia, James M., Nelson, Silke, Sokaras, Dimosthenis, Assefa, Tadesse A., Britz, Alexander, Galler, Andreas, Gawelda, Wojciech, Bressler, Christian, Gaffney, Kelly J., Lemke, Henrik T., Moller, Klaus B., Nielsen, Martin M., Sundstrom, Villy, Vanko, Gyorgy, Warnmark, Kenneth, Canton, Sophie E., & Haldrup, Kristoffer. Femtosecond x-ray scattering study of ultrafast photoinduced structural dynamics in solvated [Co(terpy)2]2+. United States. doi:10.1103/PhysRevLett.117.013002.
Biasin, Elisa, van Driel, Tim Brandt, Kjær, Kasper S., Dohn, Asmus O., Christensen, Morten, Harlang, Tobias, Chabera, Pavel, Liu, Yizhu, Uhlig, Jens, Papai, Matyas, Nemeth, Zoltan, Hartsock, Robert, Liang, Winnie, Zhang, Jianxin, Alonso-Mori, Roberto, Chollet, Matthieu, Glownia, James M., Nelson, Silke, Sokaras, Dimosthenis, Assefa, Tadesse A., Britz, Alexander, Galler, Andreas, Gawelda, Wojciech, Bressler, Christian, Gaffney, Kelly J., Lemke, Henrik T., Moller, Klaus B., Nielsen, Martin M., Sundstrom, Villy, Vanko, Gyorgy, Warnmark, Kenneth, Canton, Sophie E., and Haldrup, Kristoffer. Thu . "Femtosecond x-ray scattering study of ultrafast photoinduced structural dynamics in solvated [Co(terpy)2]2+". United States. doi:10.1103/PhysRevLett.117.013002. https://www.osti.gov/servlets/purl/1335954.
@article{osti_1335954,
title = {Femtosecond x-ray scattering study of ultrafast photoinduced structural dynamics in solvated [Co(terpy)2]2+},
author = {Biasin, Elisa and van Driel, Tim Brandt and Kjær, Kasper S. and Dohn, Asmus O. and Christensen, Morten and Harlang, Tobias and Chabera, Pavel and Liu, Yizhu and Uhlig, Jens and Papai, Matyas and Nemeth, Zoltan and Hartsock, Robert and Liang, Winnie and Zhang, Jianxin and Alonso-Mori, Roberto and Chollet, Matthieu and Glownia, James M. and Nelson, Silke and Sokaras, Dimosthenis and Assefa, Tadesse A. and Britz, Alexander and Galler, Andreas and Gawelda, Wojciech and Bressler, Christian and Gaffney, Kelly J. and Lemke, Henrik T. and Moller, Klaus B. and Nielsen, Martin M. and Sundstrom, Villy and Vanko, Gyorgy and Warnmark, Kenneth and Canton, Sophie E. and Haldrup, Kristoffer},
abstractNote = {Here, we study the structural dynamics of photoexcited [Co(terpy)2]2+ in an aqueous solution with ultrafast x-ray diffuse scattering experiments conducted at the Linac Coherent Light Source. Through direct comparisons with density functional theory calculations, our analysis shows that the photoexcitation event leads to elongation of the Co-N bonds, followed by coherent Co-N bond length oscillations arising from the impulsive excitation of a vibrational mode dominated by the symmetrical stretch of all six Co-N bonds. This mode has a period of 0.33 ps and decays on a subpicosecond time scale. We find that the equilibrium bond-elongated structure of the high spin state is established on a single-picosecond time scale and that this state has a lifetime of ~7 ps.},
doi = {10.1103/PhysRevLett.117.013002},
journal = {Physical Review Letters},
number = 1,
volume = 117,
place = {United States},
year = {2016},
month = {6}
}

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    Works referencing / citing this record:

    Spectroscopic, Structural, and Kinetic Investigation of the Ultrafast Spin Crossover in an Unusual Cobalt(II) Semiquinonate Radical Complex
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