Cavity catalysis: modifying linear free-energy relationship under cooperative vibrational strong coupling

Abstract

Here, we used an unconventional idea of cooperative vibrational strong coupling of solute and solvent molecules to enhance the rate of an esterification reaction. Different derivatives of p-nitrophenyl benzoate (solute) and isopropyl acetate (solvent) are cooperatively coupled to an infrared Fabry–Perot cavity mode. The apparent rates are increased by more than six times at the ON resonance condition, and the rate enhancement follows the lineshape of the vibrational envelope. Very interestingly, a strongly coupled system doesn't obey the Hammett relations. Thermodynamics suggests that the reaction mechanism remains intact for cavity and non-cavity conditions. Temperature-dependent experiments show an entropy-driven process for the coupled molecules. Vacuum field coupling decreases the free energy of activation by 2–5 kJ mol−1, supporting a catalysis process. The non-linear rate enhancement can be due to the reshuffling of the energy distribution between the substituents and the reaction center across the aromatic ring. These findings underline the non-equilibrium behavior of cavity catalysis.

Graphical abstract: Cavity catalysis: modifying linear free-energy relationship under cooperative vibrational strong coupling

Supplementary files

Article information

Article type
Edge Article
Submitted
25 Aug 2021
Accepted
24 Nov 2021
First published
25 Nov 2021
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2022, Advance Article

Cavity catalysis: modifying linear free-energy relationship under cooperative vibrational strong coupling

J. Lather, A. N. K. Thabassum, J. Singh and J. George, Chem. Sci., 2022, Advance Article , DOI: 10.1039/D1SC04707H

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