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  Coherent ultrafast lattice-directed reaction dynamics of triiodide anion photodissociation

Xian, R., Corthey, G., Rogers, D. M., Morrison, C. A., Prokhorenko, V., Hayes, S. A., et al. (2017). Coherent ultrafast lattice-directed reaction dynamics of triiodide anion photodissociation. Nature Chemistry, 9(6), 516-522. doi:10.1038/nchem.2751.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-002C-E655-B Version Permalink: http://hdl.handle.net/21.11116/0000-0001-EADB-1
Genre: Journal Article

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https://dx.doi.org/10.1038/NCHEM.2751 (Publisher version)
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 Creators:
Xian, Rui1, Author              
Corthey, Gastón1, Author              
Rogers, David M.2, Author
Morrison, Carole A.2, Author
Prokhorenko, Valentyn1, Author              
Hayes, Stuart A.1, Author              
Miller, R. J. Dwayne1, 3, 4, Author              
Affiliations:
1Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society, ou_1938288              
2School of Chemistry and EaStCHEM Research School, University of Edinburgh, ou_persistent22              
3Departments of Chemistry and Physics, University of Toronto, ou_persistent22              
4Hamburg Center for Ultrafast Imaging, ou_persistent22              

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Free keywords: Reaction kinetics and dynamics Photochemistry Quantum chemistry Optical spectroscopy
 Abstract: Solid-state reactions are influenced by the spatial arrangement of the reactants and the electrostatic environment of the lattice, which may enable lattice-directed chemical dynamics. Unlike the caging imposed by an inert matrix, an active lattice participates in the reaction, however, little evidence of such lattice participation has been gathered on ultrafast timescales due to the irreversibility of solid-state chemical systems. Here, by lowering the temperature to 80 K, we have been able to study the dissociative photochemistry of the triiodide anion (I3−) in single-crystal tetra-n-butylammonium triiodide using broadband transient absorption spectroscopy. We identified the coherently formed tetraiodide radical anion (I4•−) as a reaction intermediate. Its delayed appearance after that of the primary photoproduct, diiodide radical I2•−, indicates that I4•− was formed via a secondary reaction between a dissociated iodine radical (I) and an adjacent I3−. This chemistry occurs as a result of the intermolecular interaction determined by the crystalline arrangement and is in stark contrast with previous solution studies.

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 Dates: 2017-02-132016-07-192017-02-132017-03-272017-06
 Publication Status: Published in print
 Pages: 7
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 Rev. Method: Peer
 Identifiers: DOI: 10.1038/nchem.2751
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Title: Nature Chemistry
Source Genre: Journal
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Publ. Info: London, UK : Nature Publishing Group
Pages: - Volume / Issue: 9 (6) Sequence Number: - Start / End Page: 516 - 522 Identifier: -