Polarizability and isotope effects on dispersion interactions in water

Zhan, Yi-Yang; Jiang, Qi-Chun; Ishii, Kentaro; Koide, Takuya; Kobayashi, Osamu; Kojima, Tatsuo; Takahashi, Satoshi; Tachikawa, Masanori; Uchiyama, Susumu; Hiraoka, Shûichi

doi:10.1038/s42004-019-0242-0

Cited by 10 publications

(7 citation statements)

References 64 publications

(88 reference statements)

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“…[55,62] Changes in solvent polarizability, polarity and dynamics under strong coupling may be at play under strong coupling. [18,19] While these can also be induced by the isotope effect as just discussed, [63,64] the difference between the isotope and the VSC effects shows that VSC induces additional changes. The most likely reason is a modification in the dispersive interactions.…”

Section: Communicationsmentioning

confidence: 98%

Supramolecular Assembly of Conjugated Polymers under Vibrational Strong Coupling

et al. 2021

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Strong coupling plays a significant role in influencing chemical reactions and tuning material properties by modifying the energy landscapes of the systems. Here we study the effect of vibrational strong coupling (VSC) on supramolecular organization. For this purpose, a rigid-rod conjugated polymer known to form gels was strongly coupled together with its solvent in a microfluidic IR Fabry-Perot cavity. Absorption and fluorescence studies indicate a large modification of the self-assembly under such cooperative VSC. Electron microscopy confirms that in this case, the supramolecular morphology is totally different from that observed in the absence of strong coupling. In addition, the self-assembly kinetics are altered and depend on the solvent vibration under VSC. The results are compared to kinetic isotope effects on the self-assembly to help clarify the role of different parameters under strong coupling. These findings indicate that VSC is a valuable new tool for controlling supramolecular assemblies with broad implications for the molecular and material sciences.

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Section: Communicationsmentioning

confidence: 98%

Supramolecular Assembly of Conjugated Polymers under Vibrational Strong Coupling

et al. 2021

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“…Changes in solvent polarizability, polarity and dynamics under strong coupling may be at play under strong coupling [18, 19] . While these can also be induced by the isotope effect as just discussed, [63, 64] the difference between the isotope and the VSC effects shows that VSC induces additional changes. The most likely reason is a modification in the dispersive interactions.…”

Section: Figurementioning

confidence: 94%

Supramolecular Assembly of Conjugated Polymers under Vibrational Strong Coupling

et al. 2021

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Strong coupling plays a significant role in influencing chemical reactions and tuning material properties by modifying the energy landscapes of the systems. Here we study the effect of vibrational strong coupling (VSC) on supramolecular organization. For this purpose, a rigid‐rod conjugated polymer known to form gels was strongly coupled together with its solvent in a microfluidic IR Fabry–Perot cavity. Absorption and fluorescence studies indicate a large modification of the self‐assembly under such cooperative VSC. Electron microscopy confirms that in this case, the supramolecular morphology is totally different from that observed in the absence of strong coupling. In addition, the self‐assembly kinetics are altered and depend on the solvent vibration under VSC. The results are compared to kinetic isotope effects on the self‐assembly to help clarify the role of different parameters under strong coupling. These findings indicate that VSC is a valuable new tool for controlling supramolecular assemblies with broad implications for the molecular and material sciences.

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“…Confinement, by influencing molecular vibrations 8 – 10 , can also lead to isotopic fractionation. While the change of properties of water confined in nanotubes has been documented some time ago 11 it is only recently that the related deuterium isotope effects have been reported 12 , 13 . Kinetics and equilibrium deuterium isotope effects on the confinement at the macroscale have also been observed in the past 14 – 17 .…”

Section: Introductionmentioning

confidence: 99%

Unprecedently large 37Cl/35Cl equilibrium isotopic fractionation on nano-confinement of chloride anion

Pokora

Paneth

2022

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Confinement can result in unusual properties leading to new, exciting discoveries in the nano-realm. One such consequence of confinement at the nanoscale is extremally large isotopic fractionation, especially at sub-van der Waals distances. Herein, on the example of chlorine isotope effects, we show that at conditions of nanoencapsulation these effects may reach values by far larger than observed for the bulk environment, which in the case of nanotubes can lead to practical applications (e.g., in isotopic enrichment) and needs to be considered in analytical procedures that employ nanomaterials.

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Polarizability and isotope effects on dispersion interactions in water

Cited by 10 publications

References 64 publications

Supramolecular Assembly of Conjugated Polymers under Vibrational Strong Coupling

Supramolecular Assembly of Conjugated Polymers under Vibrational Strong Coupling

Supramolecular Assembly of Conjugated Polymers under Vibrational Strong Coupling

Unprecedently large 37Cl/35Cl equilibrium isotopic fractionation on nano-confinement of chloride anion

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