On the Role of Symmetry in Vibrational Strong Coupling: The Case of Charge‐Transfer Complexation
| Autor: | Anoop Thomas, Cyriaque Genet, Kripa Joseph, Robrecht M. A. Vergauwe, Thomas W. Ebbesen, Kalaivanan Nagarajan, Yantao Pang, Bianca Patrahau, Kuidong Wang |
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| Přispěvatelé: | Institut de Science et d'ingénierie supramoléculaires (ISIS), Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA) |
| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: |
Physics
010405 organic chemistry [CHIM.ORGA]Chemical Sciences/Organic chemistry Communication charge transfer Perturbation (astronomy) Vibrational Strong Coupling | Hot Paper General Chemistry General Medicine 010402 general chemistry 01 natural sciences Catalysis Communications 0104 chemical sciences 3. Good health Vibration vibrations [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry Normal mode Chemical physics Strong coupling light–matter strong coupling polaritonic chemistry Equilibrium constant symmetry |
| Zdroj: | Angewandte Chemie International Edition Angewandte Chemie International Edition, Wiley-VCH Verlag, 2020, 59 (26), pp.10436-10440. ⟨10.1002/anie.202002527⟩ Angewandte Chemie (International Ed. in English) Angewandte Chemie |
| ISSN: | 1433-7851 1521-3773 |
| Popis: | It is well known that symmetry plays a key role in chemical reactivity. Here we explore its role in vibrational strong coupling (VSC) for a charge‐transfer (CT) complexation reaction. By studying the trimethylated‐benzene–I2 CT complex, we find that VSC induces large changes in the equilibrium constant KDA of the CT complex, reflecting modifications in the ΔG° value of the reaction. Furthermore, by tuning the microfluidic cavity modes to the different IR vibrations of the trimethylated benzene, ΔG° either increases or decreases depending only on the symmetry of the normal mode that is coupled. This result reveals the critical role of symmetry in VSC and, in turn, provides an explanation for why the magnitude of chemical changes induced by VSC are much greater than the Rabi splitting, that is, the energy perturbation caused by VSC. These findings further confirm that VSC is powerful and versatile tool for the molecular sciences. We built this CT: By studying the mesitylene–I2 charge transfer (CT) complex, it is shown that vibrational strong coupling induces large changes in the equilibrium constant KDA of the CT complex, which can be either enhanced or suppressed depending only on the symmetry of the vibration coupled to the vacuum electromagnetic field. |
| Databáze: | OpenAIRE |
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