title: Ground-State Chemical Reactivity under Vibrational Coupling to the Vacuum Electromagnetic Field.
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.
authors.affiliation: University of Strasbourg, CNRS, ISIS & icFRC, 8 allée G. Monge, 67000, Strasbourg, France.
authors.forename: Anoop
authors.initials: A
authors.lastname: Thomas
authors.affiliation: University of Strasbourg, CNRS, ISIS & icFRC, 8 allée G. Monge, 67000, Strasbourg, France.
authors.forename: Jino
authors.initials: J
authors.lastname: George
authors.affiliation: Braude College, Snunit St 51, Karmiel, 2161002, Israel.
authors.forename: Atef
authors.initials: A
authors.lastname: Shalabney
authors.affiliation: University of Strasbourg, CNRS, ISIS & icFRC, 8 allée G. Monge, 67000, Strasbourg, France.
authors.forename: Marian
authors.initials: M
authors.lastname: Dryzhakov
authors.affiliation: University of Strasbourg, CNRS, ISIS & icFRC, 8 allée G. Monge, 67000, Strasbourg, France.
authors.forename: Sreejith J
authors.initials: SJ
authors.lastname: Varma
authors.affiliation: University of Strasbourg, CNRS, ISIS & icFRC, 8 allée G. Monge, 67000, Strasbourg, France.
authors.forename: Joseph
authors.initials: J
authors.lastname: Moran
authors.affiliation: University of Strasbourg, CNRS, ISIS & icFRC, 8 allée G. Monge, 67000, Strasbourg, France.
authors.forename: Thibault
authors.initials: T
authors.lastname: Chervy
authors.affiliation: University of Strasbourg, CNRS, ISIS & icFRC, 8 allée G. Monge, 67000, Strasbourg, France.
authors.forename: Xiaolan
authors.initials: X
authors.lastname: Zhong
authors.affiliation: University of Strasbourg, CNRS, ISIS & icFRC, 8 allée G. Monge, 67000, Strasbourg, France.
authors.forename: Eloïse
authors.initials: E
authors.lastname: Devaux
authors.affiliation: University of Strasbourg, CNRS, ISIS & icFRC, 8 allée G. Monge, 67000, Strasbourg, France.
authors.forename: Cyriaque
authors.initials: C
authors.lastname: Genet
authors.affiliation: University of Strasbourg, CNRS, ISIS & icFRC, 8 allée G. Monge, 67000, Strasbourg, France.
authors.forename: James A
authors.initials: JA
authors.lastname: Hutchison
authors.affiliation: University of Strasbourg, CNRS, ISIS & icFRC, 8 allée G. Monge, 67000, Strasbourg, France. ebbesen@unistra.fr.
authors.forename: Thomas W
authors.initials: TW
authors.lastname: Ebbesen
keywords: IR spectroscopy; kinetics; strong coupling; thermodynamics; vibrations