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 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…

• CI
  Centre International de Recherche aux Frontières de la Chimie
• E
  Equipex
• AN
  Agence Nationale de la Recherche

  Awards: ANR-10-IDEX-, ANR-10-IDEX-0002, ANR-10-LABX-0026, 10-LABX-0026, ANR-10-IDEX, 10-IDEX-0002-02, ANR-10-LABX-0026 CSC, ANR-10, ANR-11-LABX-0058, ANR-10-EQPX-52, ANR-11-LABX-0058 NIE, ANR-10-EQPX, ANR-10-EQPX-52-01, ANR-10-IDEX-0002-02
• CS
  China Scholarship Council
• LD
  Laboratoires d'excellence Nanostructures en Interaction avec leur Environnement

  Awards: ANR-11-LABX-0058 NIE, ANR-10-IDEX-0002-02