Solvent Dependence on Cooperative Vibrational Strong Coupling and Cavity Catalysis
Jaibir Singh1, Jyoti Lather1, Jino George1
1Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER), Mohali, Punjab, 140306, India.
Summary
Cooperative vibrational strong coupling (VSC) enhances ester solvolysis reaction rates in specific solvents by modifying activation energy. This highlights VSC
Area of Science:
- Physical Chemistry
- Chemical Kinetics
- Spectroscopy
Background:
- Strong light-matter coupling, specifically vibrational strong coupling (VSC), offers novel pathways for controlling chemical reactions.
- Understanding solvent effects is crucial for optimizing reactions under VSC conditions.
- Polaritonic chemistry explores how light-matter interactions influence chemical processes.
Purpose of the Study:
- To investigate the influence of solvent choice on ester solvolysis reaction rates under cooperative VSC.
- To compare cavity catalysis effects using different solvents and reactants.
- To elucidate the role of solvent VSC in modifying reaction activation free energy.
Main Methods:
- Studied solvolysis rates of para-nitrophenylacetate, 3-methyl-para-nitrophenylbenzoate, and bis-(2, 4-dinitrophenyl) oxalate.
- Employed ethyl acetate and cyclopentanone as solvents within a Fabry-Perot cavity.
- Performed thermodynamic studies and cavity detuning experiments to analyze VSC effects.
Main Results:
- Both ethyl acetate and cyclopentanone enhanced reaction rates for specific esters under cooperative VSC.
- Resonance effects were observed at different temperatures for each solvent, confirmed by thermodynamic data.
- Bis-(2, 4-dinitrophenyl) oxalate showed no response to VSC due to poor vibrational band overlap.
Conclusions:
- Cooperative VSC of the solvent significantly influences ester solvolysis rates by altering activation free energy.
- Solvent properties and vibrational mode overlap are critical for effective VSC-mediated reaction control.
- The findings strongly support the principles of polaritonic chemistry in reaction modification.
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