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Hauptverfasser: Chen, Liying, Fidler, Ashley P., McKillop, Alexander M., Weichman, Marissa L.
Format: Preprint
Veröffentlicht: 2023
Schlagworte:
Online-Zugang:https://arxiv.org/abs/2310.19133
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author Chen, Liying
Fidler, Ashley P.
McKillop, Alexander M.
Weichman, Marissa L.
author_facet Chen, Liying
Fidler, Ashley P.
McKillop, Alexander M.
Weichman, Marissa L.
contents 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$.
format Preprint
id arxiv_https___arxiv_org_abs_2310_19133
institution arXiv
publishDate 2023
record_format arxiv
spellingShingle Exploring the impact of vibrational cavity coupling strength on ultrafast CN + $c$-C$_6$H$_{12}$ reaction dynamics
Chen, Liying
Fidler, Ashley P.
McKillop, Alexander M.
Weichman, Marissa L.
Chemical Physics
Quantum Physics
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$.
title Exploring the impact of vibrational cavity coupling strength on ultrafast CN + $c$-C$_6$H$_{12}$ reaction dynamics
topic Chemical Physics
Quantum Physics
url https://arxiv.org/abs/2310.19133