Tilting a ground-state reactivity landscape by vibrational strong coupling

By Anoop Thomas, Lucas Lethuillier-Karl, Kalaivanan Nagarajan, Robrecht M. A. Vergauwe, Jino George, T. Chervy, Atef Shalabney, É. Devaux, C. Genet, Joseph Moran and 1 more. Science, 2018

729 citations recorded by the source corpus.

Shaking up reaction-site selectivity It seems intuitive that putting vibrational energy into a chemical bond ought to promote selective cleavage of that bond. In fact, the relation of vibrational excitation to reactivity has generally proven subtler and more complex. Thomas et al. studied how strong coupling of specific vibrational modes to an optical cavity might influence a molecule with two competing reactive sites. The molecule had two silicon centers that could react with fluoride by respective cleavage of a Si–C or Si–O bond. Exciting the vibrations at either center slowed down the overall reaction while favoring otherwise disfavored Si–O cleavage. Science, this issue p. 615 Strong coupling of vibrational modes to an optical cavity shifts site-selectivity in competing silyl substitution reactions. Many chemical methods have been developed to favor a particular product in transformations of compounds that have two or more reactive sites. We explored a different approach to site selectivity using vibrational strong coupling (VSC) between a reactant and the vacuum field of a microfluidic optical cavity. Specifically, we studied the reactivity of a compound bearing two possible silyl bond cleavage sites—Si–C and Si–O, respectively—as a function of VSC of three distinct vibrational modes in the dark. The results show that VSC can indeed tilt the reactivity landscape to favor one product over the other. Thermodynamic parameters reveal the presence of a large activation barrier and substantial changes to the activation entropy, confirming the modified chemical landscape under strong coupling.

Subfields: Atomic and Molecular Physics, and Optics

View Paper: https://www.semanticscholar.org/paper/594d2e2eba4dfb5bb1cf1dfef759a8d6c4b48eed

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In Atomic and Molecular Physics, and Optics

1. F. García-Vidal
2. T. Ebbesen
3. J. Feist
4. Javier Galego
5. C. Climent
6. E. Demler
7. C. Ciuti
8. Á. Rubio

Citations in the corpus

• Cavity Casimir-Polder Forces and Their Effects in Ground-State Chemical Reactivity (2018, background): “, the case which corresponds to the experimentally used Fabry-Perot cavities with in-plane dispersion [14,37].”
• Bimetallic nanostructures: combining plasmonic and catalytic metals for photocatalysis (2019, background): “When these gaps are shrunk to atomic scales (‘picocavities’), the high field localization leads to strong coupling between the molecule and the plasmonic cavity modes, potentially modifying the energetics for bond dissociation [58] or changing reaction pathways via Rabi splitting, similar to what ha”
• Quantum Electrodynamic Control of Matter: Cavity-Enhanced Ferroelectric Phase Transition (2020, background): “In both areas, cavity setups have been discussed as a platform to modify a broad range of physical properties, including superconductivity [100–102], charge and energy transport [103– 110], hybridized excitations in molecular crystals [111–114] and light-harvesting complexes [115], and chemical reac”
• Coupled Cluster Theory for Molecular Polaritons: Changing Ground and Excited States (2020, background): “In particular, Ebbesen and co-workers have found that strong coupling to vibrational excited states in molecules can inhibit [13–15], catalyze [16,17], and induce selective change in the reactive path of a chemical reaction [18].”
• Manipulating matter by strong coupling to vacuum fields (2021, methodology): “Chemical landscapes can be tilted toward a desired product, and only VSC of vibrations closely linked to the bonds breaking induce an effect (97).”