Premium
Cavity Catalysis by Cooperative Vibrational Strong Coupling of Reactant and Solvent Molecules
Author(s) -
Lather Jyoti,
Bhatt Pooja,
Thomas Anoop,
Ebbesen Thomas W.,
George Jino
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201905407
Subject(s) - catalysis , chemistry , solvent , kinetic isotope effect , molecule , rotational–vibrational coupling , molecular vibration , reaction rate , photochemistry , solvolysis , chemical physics , computational chemistry , deuterium , organic chemistry , atomic physics , hydrolysis , physics
Here, we report the catalytic effect of vibrational strong coupling (VSC) on the solvolysis of para ‐nitrophenyl acetate (PNPA), which increases the reaction rate by an order of magnitude. This is observed when the microfluidic Fabry–Perot cavity in which the VSC is generated is tuned to the C=O vibrational stretching mode of both the reactant and solvent molecules. Thermodynamic experiments confirm the catalytic nature of VSC in the system. The change in the reaction rate follows an exponential relation with respect to the coupling strength of the solvent, indicating a cooperative effect between the solvent molecules and the reactant. Furthermore, the study of the solvent kinetic isotope effect clearly shows that the vibrational overlap of the C=O vibrational bands of the reactant and the strongly coupled solvent molecules is critical for the catalysis in this reaction. The combination of cooperative effects and cavity catalysis confirms the potential of VSC as a new frontier in chemistry.