Advanced

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

Van Driel, Tim B.; Kjaer, Kasper S. LU ; Hartsock, Robert W.; Dohn, Asmus O.; Harlang, Tobias LU ; Chollet, Matthieu; Christensen, Morten; Gawelda, Wojciech; Henriksen, Niels E. and Kim, Jong Goo, et al. (2016) In Nature Communications 7.
Abstract

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 [Ir 2 (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... (More)

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 [Ir 2 (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.

(Less)
Please use this url to cite or link to this publication:
author
, et al. (More)
(Less)
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Nature Communications
volume
7
publisher
Nature Publishing Group
external identifiers
  • scopus:85000843958
  • wos:000388643800001
ISSN
2041-1723
DOI
10.1038/ncomms13678
language
English
LU publication?
yes
id
d804707e-18c0-4613-84d3-c5084cd9e757
date added to LUP
2016-12-19 12:18:21
date last changed
2017-10-01 05:27:47
@article{d804707e-18c0-4613-84d3-c5084cd9e757,
  abstract     = {<p>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 [Ir 2 (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.</p>},
  articleno    = {13678},
  author       = {Van Driel, Tim B. and Kjaer, Kasper S. and Hartsock, Robert W. and Dohn, Asmus O. and Harlang, Tobias and Chollet, Matthieu and Christensen, Morten and Gawelda, Wojciech and Henriksen, Niels E. and Kim, Jong Goo and Haldrup, Kristoffer and Kim, Kyung Hwan and Ihee, Hyotcherl and Kim, Jeongho and Lemke, Henrik and Sun, Zheng and Sundström, Villy and Zhang, Wenkai and Zhu, Diling and MØller, Klaus B. and Nielsen, Martin M. and Gaffney, Kelly J.},
  issn         = {2041-1723},
  language     = {eng},
  month        = {11},
  publisher    = {Nature Publishing Group},
  series       = {Nature Communications},
  title        = {Atomistic characterization of the active-site solvation dynamics of a model photocatalyst},
  url          = {http://dx.doi.org/10.1038/ncomms13678},
  volume       = {7},
  year         = {2016},
}