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Ground‐State Chemical Reactivity under Vibrational Coupling to the Vacuum Electromagnetic Field
Author(s) -
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.
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201605504
Subject(s) - chemistry , rotational–vibrational coupling , enthalpy , ground state , coupling (piping) , chemical reaction , molecular vibration , zero point energy , electromagnetic field , kinetic energy , vibrational energy , reaction rate , atomic physics , chemical physics , molecular physics , thermodynamics , infrared spectroscopy , materials science , molecule , physics , organic chemistry , quantum mechanics , metallurgy , catalysis
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.