Exploring the impact of vibrational cavity coupling strength on ultrafast CN + $c$-C${}_6$H${}_{12}$ reaction dynamics

Abstract

Molecular polaritons, hybrid light-matter states resulting from strong cavity coupling of optical transitions, may provide a new route to guide chemical reactions. However, demonstrations of cavity-modified reactivity in clean benchmark systems are still needed to clarify the mechanisms and scope of polariton chemistry. Here, we use transient absorption to observe the ultrafast dynamics of CN radicals interacting with a cyclohexane ($c$-C${}_6$H${}_{12}$) and chloroform (CHCl${}_3$) solvent mixture under vibrational strong coupling of the brightest C$-$H stretching mode of $c$-C${}_6$H${}_{12}$. By modulating the $c$-C${}_6$H${}_{12}$:CHCl${}_3$ ratio, we explore how solvent complexation and hydrogen (H)-abstraction processes proceed under collective cavity coupling strengths ranging from 55$-$85 cm${}^{-1}$. Reaction rates remain unchanged for all extracavity, on resonance, and off-resonance cavity coupling conditions, regardless of coupling strength. These results suggest that insufficient vibrational cavity coupling strength may not be the determining factor for the negligible cavity effects observed previously in H-abstraction reactions of CN with CHCl${}_3$.

References in corpus (5)

• Strong coupling between surface plasmon polaritons and emitters
• Swinging between shine and shadow: Theoretical advances on thermally-activated vibropolaritonic chemistry (a perspective)
• Cavity-Altered Thermal Isomerization Rates and Dynamical Resonant Localization in Vibro-Polaritonic Chemistry
• Ultrafast dynamics of CN radical reactions with chloroform solvent under vibrational strong coupling
• Dissociation dynamics of a diatomic molecule in an optical cavity

Cited by in corpus (7)

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• A Cavity-Enhanced Spectroscopist's Lens on Molecular Polaritons
• On-the-Fly Cavity-Molecular Dynamics of Vibrational Polaritons
• Interplay between Static and Dynamic Disorder: Contrasting Effects on Dark State Population inside a Cavity
• Disorder-Induced Spectral Splitting versus Rabi Splitting under Strong Light-Matter Coupling
• Direct readout of excited state lifetimes in chlorin chromophores under electronic strong coupling
• Ultrafast optical modulation of vibrational strong coupling in ReCl(CO)${}_3$(2,2-bipyridine)