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Ground‐State Chemical Reactivity under Vibrational Coupling to the Vacuum Electromagnetic Field

The ground‐state deprotection of a simple alkynylsilane is studied under vibrational strong coupling to the zero‐point fluctuations, or vacuum electromagnetic field, of a resonant IR microfluidic cavity. The reaction rate decreased by a factor of up to 5.5 when the Si−C vibrational stretching modes...

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Detalles Bibliográficos
Autores principales: Thomas, Anoop, George, Jino, Shalabney, Atef, Dryzhakov, Marian, Varma, Sreejith J., Moran, Joseph, Chervy, Thibault, Zhong, Xiaolan, Devaux, Eloïse, Genet, Cyriaque, Hutchison, James A., Ebbesen, Thomas W.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2016
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5113700/
https://www.ncbi.nlm.nih.gov/pubmed/27529831
http://dx.doi.org/10.1002/anie.201605504
Descripción
Sumario:The ground‐state deprotection of a simple alkynylsilane is studied under vibrational strong coupling to the zero‐point fluctuations, or vacuum electromagnetic field, of a resonant IR microfluidic cavity. The reaction rate decreased by a factor of up to 5.5 when the Si−C vibrational stretching modes of the reactant were strongly coupled. The relative change in the reaction rate under strong coupling depends on the Rabi splitting energy. Product analysis by GC‐MS confirmed the kinetic results. Temperature dependence shows that the activation enthalpy and entropy change significantly, suggesting that the transition state is modified from an associative to a dissociative type. These findings show that vibrational strong coupling provides a powerful approach for modifying and controlling chemical landscapes and for understanding reaction mechanisms.