| 1. |
- Castagnola, Matteo, et al.
(author)
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Collective Strong Coupling Modifies Aggregation and Solvation
- 2024
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In: Journal of Physical Chemistry Letters. - 1948-7185. ; , s. 1428-1434
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Journal article (peer-reviewed)abstract
- Intermolecular (Coulombic) interactions are pivotal for aggregation, solvation, and crystallization. We demonstrate that the collective strong coupling of several molecules to a single optical mode results in notable changes in the molecular excitations around a single perturbed molecule, thus representing an impurity in an otherwise ordered system. A competition between short-range coulombic and long-range photonic correlations inverts the local transition density in a polaritonic state, suggesting notable changes in the polarizability of the solvation shell. Our results provide an alternative perspective on recent work in polaritonic chemistry and pave the way for the rigorous treatment of cooperative effects in aggregation, solvation, and crystallization.
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| 2. |
- Schäfer, Christian, 1989, et al.
(author)
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Shining light on the microscopic resonant mechanism responsible for cavity-mediated chemical reactivity
- 2022
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In: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723 .- 2041-1723. ; 13:1
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Journal article (peer-reviewed)abstract
- Strong light–matter interaction in cavity environments is emerging as a promising approach to control chemical reactions in a non-intrusive and efficient manner. The underlying mechanism that distinguishes between steering, accelerating, or decelerating a chemical reaction has, however, remained unclear, hampering progress in this frontier area of research. We leverage quantum-electrodynamical density-functional theory to unveil the microscopic mechanism behind the experimentally observed reduced reaction rate under cavity induced resonant vibrational strong light-matter coupling. We observe multiple resonances and obtain the thus far theoretically elusive but experimentally critical resonant feature for a single strongly coupled molecule undergoing the reaction. While we describe only a single mode and do not explicitly account for collective coupling or intermolecular interactions, the qualitative agreement with experimental measurements suggests that our conclusions can be largely abstracted towards the experimental realization. Specifically, we find that the cavity mode acts as mediator between different vibrational modes. In effect, vibrational energy localized in single bonds that are critical for the reaction is redistributed differently which ultimately inhibits the reaction.
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| 3. |
- Sidler, Dominik, et al.
(author)
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A perspective on ab initio modeling of polaritonic chemistry: The role of non-equilibrium effects and quantum collectivity
- 2022
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In: Journal of Chemical Physics. - : AIP Publishing. - 1089-7690 .- 0021-9606. ; 156:23
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Journal article (peer-reviewed)abstract
- This Perspective provides a brief introduction into the theoretical complexity of polaritonic chemistry, which emerges from the hybrid nature of strongly coupled light-matter states. To tackle this complexity, the importance of ab initio methods is highlighted. Based on those, novel ideas and research avenues are developed with respect to quantum collectivity, as well as for resonance phenomena immanent in reaction rates under vibrational strong coupling. Indeed, fundamental theoretical questions arise about the mesoscopic scale of quantum-collectively coupled molecules when considering the depolarization shift in the interpretation of experimental data. Furthermore, to rationalize recent findings based on quantum electrodynamical density-functional theory (QEDFT), a simple, but computationally efficient, Langevin framework is proposed based on well-established methods from molecular dynamics. It suggests the emergence of cavity-induced non-equilibrium nuclear dynamics, where thermal (stochastic) resonance phenomena could emerge in the absence of external periodic driving. Overall, we believe that the latest ab initio results indeed suggest a paradigmatic shift for ground-state chemical reactions under vibrational strong coupling from the collective quantum interpretation toward a more local, (semi)-classically and non-equilibrium dominated perspective. Finally, various extensions toward a refined description of cavity-modified chemistry are introduced in the context of QEDFT, and future directions of the field are sketched.
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