Ground-State Chemical Reactivity under Vibrational Coupling to the Vacuum Electromagnetic Field
| Autor: | Jino George, Thibault Chervy, Anoop Thomas, Atef Shalabney, James A. Hutchison, Thomas W. Ebbesen, Cyriaque Genet, Marian Dryzhakov, Eloïse Devaux, Xiaolan Zhong, Sreejith J. Varma, Joseph Moran |
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| Rok vydání: | 2016 |
| Předmět: |
Electromagnetic field
Enthalpy 02 engineering and technology 010402 general chemistry Kinetic energy 01 natural sciences Catalysis vibrations Reaction rate thermodynamics Computational chemistry strong coupling 0103 physical sciences Physics::Chemical Physics 010306 general physics Chemistry Communication Energy level splitting General Medicine General Chemistry 021001 nanoscience & nanotechnology Communications 0104 chemical sciences IR spectroscopy kinetics Chemical physics Kinetics | Hot Paper 0210 nano-technology Ground state Rotational–vibrational coupling Excitation |
| Zdroj: | Angewandte Chemie (International Ed. in English) |
| ISSN: | 1433-7851 |
| DOI: | 10.1002/anie.201605504 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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