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Title: Ultrafast X-Ray Scattering Measurements of Coherent Structural Dynamics on the Ground-State Potential Energy Surface of a Diplatinum Molecule

Abstract

We present x-ray free electron laser experiments addressing ground-state structural dynamics of the diplatinum anion Pt2POP4 following photoexcitation. The structural dynamics are tracked with < 100 fs time resolution by x-ray scattering, utilizing the anisotropic component to suppress contributions from the bulk solvent. The x-ray data exhibit a strong oscillatory component with period 0.28 ps and decay time 2.2 ps, and structural analysis of the difference signal directly shows this as arising from ground-state dynamics along the PtPt coordinate. Here, these results are compared with multiscale Born-Oppenheimer molecular dynamics simulations and demonstrate how off-resonance excitation can be used to prepare a vibrationally cold excited-state population complemented by a structure-dependent depletion of the ground-state population which subsequently evolves in time, allowing direct tracking of ground-state structural dynamics.

Authors:
 [1];  [2];  [3];  [1];  [1];  [1];  [4];  [3];  [5];  [2];  [6];  [6];  [6];  [7];  [1];  [6];  [1];  [1];  [1]
  1. Technical Univ. of Denmark, Lyngby (Denmark)
  2. Technical Univ. of Denmark, Lyngby (Denmark); Science Inst. of the Univ. of Iceland, Reykjavik (Iceland)
  3. Technical Univ. of Denmark, Lyngby (Denmark); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. Technical Univ. of Denmark, Lyngby (Denmark); Lund Univ., Lund (Sweden); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  5. Technical Univ. of Denmark, Lyngby (Denmark); Lund Univ., Lund (Sweden)
  6. SLAC National Accelerator Lab. (SLAC), Menlo Park, CA (United States)
  7. SLAC National Accelerator Lab. (SLAC), Menlo Park, CA (United States); Paul Scherrer Inst. (PSI), Villigen (Switzerland)
Publication Date:
Research Org.:
SLAC National Accelerator Lab. (SLAC), Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1504721
Alternate Identifier(s):
OSTI ID: 1494658
Grant/Contract Number:  
DFF-4002-00272; DFF-8021-00347B; AC02-76SF00515; 174244-051
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Letters
Additional Journal Information:
Journal Volume: 122; Journal Issue: 6; Journal ID: ISSN 0031-9007
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Haldrup, Kristoffer, Levi, Gianluca, Biasin, Elisa, Vester, Peter, Laursen, Mads Goldschmidt, Beyer, Frederik, Kjær, Kasper Skov, Brandt van Driel, Tim, Harlang, Tobias, Dohn, Asmus O., Hartsock, Robert J., Nelson, Silke, Glownia, James M., Lemke, Henrik T., Christensen, Morten, Gaffney, Kelly J., Henriksen, Niels E., Møller, Klaus B., and Nielsen, Martin M. Ultrafast X-Ray Scattering Measurements of Coherent Structural Dynamics on the Ground-State Potential Energy Surface of a Diplatinum Molecule. United States: N. p., 2019. Web. doi:10.1103/physrevlett.122.063001.
Haldrup, Kristoffer, Levi, Gianluca, Biasin, Elisa, Vester, Peter, Laursen, Mads Goldschmidt, Beyer, Frederik, Kjær, Kasper Skov, Brandt van Driel, Tim, Harlang, Tobias, Dohn, Asmus O., Hartsock, Robert J., Nelson, Silke, Glownia, James M., Lemke, Henrik T., Christensen, Morten, Gaffney, Kelly J., Henriksen, Niels E., Møller, Klaus B., & Nielsen, Martin M. Ultrafast X-Ray Scattering Measurements of Coherent Structural Dynamics on the Ground-State Potential Energy Surface of a Diplatinum Molecule. United States. doi:10.1103/physrevlett.122.063001.
Haldrup, Kristoffer, Levi, Gianluca, Biasin, Elisa, Vester, Peter, Laursen, Mads Goldschmidt, Beyer, Frederik, Kjær, Kasper Skov, Brandt van Driel, Tim, Harlang, Tobias, Dohn, Asmus O., Hartsock, Robert J., Nelson, Silke, Glownia, James M., Lemke, Henrik T., Christensen, Morten, Gaffney, Kelly J., Henriksen, Niels E., Møller, Klaus B., and Nielsen, Martin M. Wed . "Ultrafast X-Ray Scattering Measurements of Coherent Structural Dynamics on the Ground-State Potential Energy Surface of a Diplatinum Molecule". United States. doi:10.1103/physrevlett.122.063001. https://www.osti.gov/servlets/purl/1504721.
@article{osti_1504721,
title = {Ultrafast X-Ray Scattering Measurements of Coherent Structural Dynamics on the Ground-State Potential Energy Surface of a Diplatinum Molecule},
author = {Haldrup, Kristoffer and Levi, Gianluca and Biasin, Elisa and Vester, Peter and Laursen, Mads Goldschmidt and Beyer, Frederik and Kjær, Kasper Skov and Brandt van Driel, Tim and Harlang, Tobias and Dohn, Asmus O. and Hartsock, Robert J. and Nelson, Silke and Glownia, James M. and Lemke, Henrik T. and Christensen, Morten and Gaffney, Kelly J. and Henriksen, Niels E. and Møller, Klaus B. and Nielsen, Martin M.},
abstractNote = {We present x-ray free electron laser experiments addressing ground-state structural dynamics of the diplatinum anion Pt2POP4 following photoexcitation. The structural dynamics are tracked with < 100 fs time resolution by x-ray scattering, utilizing the anisotropic component to suppress contributions from the bulk solvent. The x-ray data exhibit a strong oscillatory component with period 0.28 ps and decay time 2.2 ps, and structural analysis of the difference signal directly shows this as arising from ground-state dynamics along the PtPt coordinate. Here, these results are compared with multiscale Born-Oppenheimer molecular dynamics simulations and demonstrate how off-resonance excitation can be used to prepare a vibrationally cold excited-state population complemented by a structure-dependent depletion of the ground-state population which subsequently evolves in time, allowing direct tracking of ground-state structural dynamics.},
doi = {10.1103/physrevlett.122.063001},
journal = {Physical Review Letters},
number = 6,
volume = 122,
place = {United States},
year = {2019},
month = {2}
}

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    Ultrafast structural dynamics of photo-reactions observed by time-resolved x-ray cross-correlation analysis
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