Journal article
Atomistic characterization of the active-site solvation dynamics of a model photocatalyst
Department of Physics, Technical University of Denmark1
Neutrons and X-rays for Materials Physics, Department of Physics, Technical University of Denmark2
Stanford University3
Department of Chemistry, Technical University of Denmark4
SLAC National Accelerator Laboratory5
Jan Kochanowski University in Kielce6
Korea Advanced Institute of Science and Technology7
Inha University8
Lund University9
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.
Language: | English |
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Publisher: | Nature Publishing Group |
Year: | 2016 |
Pages: | 13678 |
ISSN: | 20411723 |
Types: | Journal article |
DOI: | 10.1038/ncomms13678 |
ORCIDs: | 0000-0002-6626-7301 , 0000-0003-0397-5965 , 0000-0003-4085-293X , Nielsen, Martin Meedom , Kjær, Kasper Skov , Dohn, Asmus Ougaard , Henriksen, Niels Engholm , Haldrup, Kristoffer and Møller, Klaus Braagaard |