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- Title
Ground-State Chemical Reactivity under Vibrational Coupling to the Vacuum Electromagnetic Field.
- Authors
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.
- Abstract
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.
- Subjects
ELECTROMAGNETIC fields; REACTIVITY (Chemistry); ZERO-point field; MICROFLUIDIC analytical techniques; COUPLING reactions (Chemistry); CHEMICAL reactions
- Publication
Angewandte Chemie International Edition, 2016, Vol 55, Issue 38, p11462
- ISSN
1433-7851
- Publication type
Article
- DOI
10.1002/anie.201605504