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Title: Atomistic characterization of the active-site solvation dynamics of a model photocatalyst

Journal Article · · Nature Communications
DOI:https://doi.org/10.1038/ncomms13678· OSTI ID:1349102
 [1];  [2];  [3];  [4];  [5];  [6]; ORCiD logo [7];  [8];  [7];  [9];  [7];  [10]; ORCiD logo [9]; ORCiD logo [11];  [12];  [3];  [13];  [14];  [6];  [7] more »; ORCiD logo [7];  [3] « less
  1. Technical Univ. of Denmark (Denmark); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. Technical Univ. of Denmark (Denmark); SLAC National Accelerator Lab. and Stanford Univ., Stanford, CA (United States); Lund Univ. (Sweden)
  3. SLAC National Accelerator Lab. and Stanford Univ., Stanford, CA (United States)
  4. Technical Univ. of Denmark (Denmark); Science Institute of the Univ. of Iceland (Iceland)
  5. Technical Univ. of Denmark (Denmark); Lund Univ. (Sweden)
  6. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  7. Technical Univ. of Denmark (Denmark)
  8. European XFEL GmbH (Germany); Jan Kochanowski Univ. (Poland)
  9. KAIST (South Korea); Institute for Basic Science (South Korea)
  10. KAIST (South Korea); Institute for Basic Science (South Korea); Stockholm Univ. (Sweden)
  11. Inha Univ. (South Korea)
  12. SLAC National Accelerator Lab., Menlo Park, CA (United States); Paul Scherrer Inst. (PSI), Villigen (Switzerland)
  13. Lund Univ. (Sweden)
  14. SLAC National Accelerator Lab. and Stanford Univ., Stanford, CA (United States); Beijing Normal Univ. (China)
+ Show Author Affiliations

The interactions between the reactive excited state of molecular photocatalysts and surrounding solvent dictate reaction mechanisms and pathways, but are not readily accessible to conventional optical spectroscopic techniques. Here we report an investigation of the structural and solvation dynamics following excitation of a model photocatalytic molecular system [Ir2(dimen)4]2+, where dimen is para-diisocyanomenthane. The time-dependent structural changes in this model photocatalyst, as well as the changes in the solvation shell structure, have been measured with ultrafast diffuse X-ray scattering and simulated with Born-Oppenheimer Molecular Dynamics. Both methods provide direct access to the solute-solvent pair distribution function, enabling the solvation dynamics around the catalytically active iridium sites to be robustly characterized. Our results provide evidence for the coordination of the iridium atoms by the acetonitrile solvent and demonstrate the viability of using diffuse X-ray scattering at free-electron laser sources for studying the dynamics of photocatalysis.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-76SF00515; AC02-76SF0051
OSTI ID:
1349102
Alternate ID(s):
OSTI ID: 1527009
Journal Information:
Nature Communications, Vol. 7; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 62 works
Citation information provided by
Web of Science

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Cited By (22)

Electronic Coherence in Ultrafast X-Ray Scattering from Molecular Wave Packets journal February 2019
Solvent-dependent complex reaction pathways of bromoform revealed by time-resolved X-ray solution scattering and X-ray transient absorption spectroscopy journal November 2019
Chemical interactions and dynamics with femtosecond X-ray spectroscopy and the role of X-ray free-electron lasers journal April 2019
Initial metal–metal bond breakage detected by fs X-ray scattering in the photolysis of Ru 3 (CO) 12 in cyclohexane at 400 nm journal January 2019
Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering journal January 2020
Ultrafast structural dynamics of photo-reactions observed by time-resolved x-ray cross-correlation analysis journal March 2019
On the interplay of solvent and conformational effects in simulated excited-state dynamics of a copper phenanthroline photosensitizer journal January 2020
Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering text January 2020
Perspective: Opportunities for ultrafast science at SwissFEL text January 2017
Excited-State Solvation Structure of Transition Metal Complexes from Molecular Dynamics Simulations and Assessment of Partial Atomic Charge Methods text January 2018
Protein Structural Dynamics of Wild-Type and Mutant Homodimeric Hemoglobin Studied by Time-Resolved X-Ray Solution Scattering journal November 2018
The restricted active space followed by second-order perturbation theory method: Theory and application to the study of CuO2 and Cu2O2 systems journal May 2008
Initial metal-metal bond breakage detected by fs X-ray scattering in the photolysis of Ru3(CO)12 in cyclohexane at 400 nm text January 2019
Perspective: Opportunities for ultrafast science at SwissFEL text January 2017
Recent Advances in Ultrafast Structural Techniques journal April 2019
Perspective: Opportunities for ultrafast science at SwissFEL journal November 2017
Interfacing CRYSTAL/AMBER to Optimize QM/MM Lennard–Jones Parameters for Water and to Study Solvation of TiO2 Nanoparticles journal November 2018
Simulation of ultrafast excited-state dynamics and elastic x-ray scattering by quantum wavepacket dynamics journal September 2019
Ultrafast structural dynamics of photo-reactions observed by time-resolved x-ray cross-correlation analysis text January 2019
Scientific instrument Femtosecond X-ray Experiments (FXE): instrumentation and baseline experimental capabilities journal August 2019
Chemical interactions and dynamics with femtosecond X-ray spectroscopy and the role of X-ray free-electron lasers text January 2019
Fingerprints of electronic, spin and structural dynamics from resonant inelastic soft X-ray scattering in transient photo-chemical species text January 2019

Figures / Tables (3)

Figure 1(p. 2)figure Figure 1
Figure 2(p. 4)figure Figure 2
Figure 3(p. 5)figure Figure 3

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Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
excited states
photocatalysis