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arXiv · 2307.04875

Ultrafast dynamics of CN radical reactions with chloroform solvent under vibrational strong coupling

Ashley P. Fidler·Liying Chen·Alexander M. McKillop·Marissa L. Weichman
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Abstract

Polariton chemistry may provide a new means to control molecular reactivity, permitting remote, reversible modification of reaction energetics, kinetics, and product yields. A considerable body of experimental and theoretical work has already demonstrated that strong coupling between a molecular vibrational mode and the confined electromagnetic field of an optical cavity can alter chemical reactivity without external illumination. However, the mechanisms underlying cavity-altered chemistry remain unclear in large part because the experimental systems examined previously are too complex for detailed analysis of their reaction dynamics. Here, we experimentally investigate photolysis-induced reactions of cyanide (CN) radicals with strongly-coupled chloroform (CHCl$_3$) solvent molecules and examine the intracavity rates of photofragment recombination, solvent complexation, and hydrogen abstraction. We use a microfluidic optical cavity fitted with dichroic mirrors to facilitate vibrational strong coupling (VSC) of the C-H stretching mode of CHCl$_3$ while simultaneously permitting optical access at visible wavelengths. Ultrafast transient absorption experiments performed with cavities tuned on- and off-resonance reveal that VSC of the CHCl$_3$ C-H stretching transition does not significantly modify any measured rate constants, including those associated with the hydrogen abstraction reaction. This work represents, to the best of our knowledge, the first experimental study of an elementary bimolecular reaction under VSC. We discuss how the conspicuous absence of cavity-altered effects in this system may provide insights into the mechanisms of modified ground state reactivity under VSC and help bridge the divide between experimental results and theoretical predictions in vibrational polariton chemistry.

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Ashley P. Fidler, Liying Chen, Alexander M. McKillop, Marissa L. Weichman. 2023-10-19. Ultrafast dynamics of CN radical reactions with chloroform solvent under vibrational strong coupling. https://doi.org/10.1063/5.0167410

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