Ground state chemistry under vibrational strong coupling: dependence of thermodynamic parameters on the Rabi splitting energy

Vibrational strong coupling (VSC) is currently emerging as a tool to control chemical dynamics. Here we study the impact of strong coupling strength, given by the Rabi splitting energy ( ), on the thermodynamic parameters associated with the transition state of the desilylation reaction of the model...

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Published in:Nanophotonics (Berlin, Germany) Germany), 2020-02, Vol.9 (2), p.249-255
Main Authors: Thomas, Anoop, Jayachandran, Anjali, Lethuillier-Karl, Lucas, Vergauwe, Robrecht M.A., Nagarajan, Kalaivanan, Devaux, Eloise, Genet, Cyriaque, Moran, Joseph, Ebbesen, Thomas W.
Format: Article
Language:English
Subjects:
Activation analysis
chemical dynamics
Chemical Sciences
Coupling
Enthalpy
Entropy of activation
Free energy
microcavities
or physical chemistry
Organic chemistry
Parameters
Splitting
Temperature dependence
Theoretical and
thermodynamics
transition states
vibrational strong coupling
vibrations
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Summary:Vibrational strong coupling (VSC) is currently emerging as a tool to control chemical dynamics. Here we study the impact of strong coupling strength, given by the Rabi splitting energy ( ), on the thermodynamic parameters associated with the transition state of the desilylation reaction of the model molecule 1-phenyl-2-trimethylsilylacetylene. Under VSC, the enthalpy and entropy of activation determined from the temperature-dependent kinetic studies varied nonlinearly with the coupling strength. The thermodynamic parameters of the noncavity reaction did not show noticeable variation, ruling out concentration effects other than the enhanced for the changes observed under VSC. The difference between the total free energy change under VSC and in noncavity was relatively smaller possibly because the enthalpy and entropy of activation compensate each other. This thermodynamic study gives more insight into the role of collective strong coupling on the transition state that leads to modified dynamics and branching ratios.
ISSN:2192-8614
2192-8606
2192-8614
DOI:10.1515/nanoph-2019-0340