Selective crystallization <i>via</i> vibrational strong coupling

Hirai, Kenji; Ishikawa, Hiromasa; Chervy, Thibault; Hutchison, James A.; Uji‐i, Hiroshi

doi:10.1039/d1sc03706d

Cited by 46 publications

(81 citation statements)

References 38 publications

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“…55 Vibrational strong coupling of water was observable even by use of sixth or seventh order of cavity mode, where the effect of overdamping seems to be not negligible. 33,38,39,44,56 Thus, the overdamping could also contribute to the apparent shift of ω vib in the present system. Another possible origin of the vibrational frequency shift observed here is related to the modification of the hydration structure of water in cavity.…”

Section: ■ Results and Discussionmentioning

confidence: 76%

“…This type of complex coupling mode was observed for a higher order cavity mode with a high Rabi splitting frequency. 33,44 The bending mode at 1600 cm −1 was coupled to the cavity mode at 1750 cm −1 . As a result, the upper polariton and the lower polariton were observed at 1880 and 1460 cm −1 , respectively, with a narrower Rabi splitting frequency than that of the O−H stretching mode.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…11−16 This concept can also be applied to the vibrational states of molecules; placing molecules in a microscale cavity induces the vibro-polaritonic states, 17−27 which leads to modification of the ground-state thermochemical reactivity via vacuum vibrational coupling. 28−39 This vacuum vibrational strong coupling is also used to modify Raman scattering, 40,41 vibro-polaritonic infrared (IR) emissions, 42 the self-assembly of molecules, 43,44 ferromagnetism, 45 and even the superconductivity of materials. 46 Recently, we also investigated the use of vacuum vibrational coupling to modify the proton conductivity of aqueous electrolyte solutions.…”

Section: ■ Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Vibrational Coupling of Water from Weak to Ultrastrong Coupling Regime via Cavity Mode Tuning

2021

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Vibrational strong coupling is an emerging method for modulation of ground-state molecular properties. Spectroscopic information about the vibrational coupling state is essential for determination of the physicochemical properties of molecules coupled to vacuum electromagnetic fields. However, a systematic study of the effect of the cavity mode with respect to the coupling strength is still required. Here, we show the effect of the cavity mode on the vibrational coupling behavior of water molecules when tuned from a weak coupling regime to an ultrastrong coupling regime. The cavity thickness was controlled mechanically for modulation of the cavity mode frequency. The concentration-dependent Rabi splitting behavior is a critical for determination of the coupling behavior of water molecules to vacuum fields. We also showed the advantages of use of thinner cells for clear spectroscopic investigation of the coupling states and the possibility of modulation of the hydration environment based on cavity control. In addition, we provide the fundamental cavity mode-dependent structure relationship for the controlled molecular properties within a wide coupling strength regime.

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Section: ■ Results and Discussionmentioning

confidence: 76%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Vibrational Coupling of Water from Weak to Ultrastrong Coupling Regime via Cavity Mode Tuning

2021

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“…On the other hand, Hirai and co-workers investigated the polymorphism in metal organic frameworks crystallization under VSC of solvent molecules. 90 Preparation of Zeolitic imidazolate framework (ZIF) from aqueous solution of Zn(NO 3 ) 2 and 2methylimidazole leads to dimorphic structures (ZIF-8 and ZIF-L) under non-cavity conditions.…”

Section: Intermolecular Interactions and Supramolecular Assemblymentioning

confidence: 99%

Chemistry under Vibrational Strong Coupling

2021

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Over the past decade, the possibility of manipulating chemistry and material properties using hybrid light-matter states has stimulated considerable interest. Hybrid light-matter states can be generated by placing molecules in an optical cavity that is resonant with a molecular transition. Importantly, the hybridization occurs even in the dark because the coupling process involves the zero-point fluctuations of the optical mode (a.k.a. vacuum field) and the molecular transition. In other words, unlike photochemistry, no real photon is required to induce this strong coupling phenomenon. Strong coupling in general, but vibrational strong coupling (VSC) in particular, offers exciting possibilities for molecular and more generally material science. It is not only a new tool to control chemical reactivity but it also gives insight into which vibrations are involved in a reaction. This perspective gives the underlying fundamentals of light-matter strong coupling, including a mini-tutorial on the practical issues to achieve VSC. Recent advancement of 'vibro-polaritonic chemistry' and related topics are presented with the challenges for this exciting new field.

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“…Inspired by this seminal observation 13 from the Ebbesen group, intensive experimental and theoretical efforts have now been made to understand VSCrelated chemistry. From an experimental point of view, there has been an extensive exploration of VSC catalytic effects in different types of chemical reactions [14][15][16][17][18][19][20] and the use of VSC to alter other molecular properties in the absence of an external laser pumping 21 has also been investigated; at the same time, spectroscopists have also focused on the ultrafast dynamics of vibrational polaritons by pump-probe 22,23 and two-dimensional infrared (IR) [24][25][26][27][28][29] spectroscopies. From a theoretical point of view, while the detailed mechanism of "VSC catalysis" is still not well understood [30][31][32][33][34][35][36][37][38] , the current models of ultrafast polariton dynamics appear to be largely consistent with observations [39][40][41][42][43][44][45] .…”

Section: Introductionmentioning

confidence: 99%

Polariton relaxation under vibrational strong coupling: Comparing cavity molecular dynamics simulations against Fermi's golden rule rate

Li,

Nitzan,

Subotnik

2021

Preprint

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Under vibrational strong coupling (VSC), the formation of molecular polaritons may significantly modify the photo-induced or thermal properties of molecules. In an effort to understand these intriguing modifications, both experimental and theoretical studies have focused on the ultrafast dynamics of vibrational polaritons. Here, following our recent work [J. Chem. Phys., 154, 094124, (2021)], we systematically study the mechanism of polariton relaxation for liquid CO 2 under a weak external pumping. Classical cavity molecular dynamics (CavMD) simulations show that polariton relaxation results from the combined effects of (i) cavity loss through the photonic component and (ii) dephasing of the bright-mode component to vibrational dark modes as mediated by intermolecular interactions. The latter polaritonic dephasing rate is proportional to the product of the weight of the bright mode in the polariton wave function and the spectral overlap between the polariton and dark modes. Both these factors are sensitive to parameters such as the Rabi splitting and cavity mode detuning. Compared with a Fermi's golden rule calculation based on a tight-binding harmonic model, CavMD yields similar parameter dependence for the upper polariton relaxation lifetime but sometimes a modest disagreement for the lower polariton. We suggest that this disagreement results from polariton-enhanced molecular nonlinear absorption due to molecular anharmonicity, which is not included in our analytical model. We also summarize recent progress on probing nonreactive VSC dynamics with CavMD.

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Selective crystallization via vibrational strong coupling

Abstract: The coupling of (photo)chemical processes to optical cavity vacuum fields is an emerging method for modulating molecular and material properties. Recent reports have shown that strong coupling of the vibrational...

Cited by 46 publications

References 38 publications

Vibrational Coupling of Water from Weak to Ultrastrong Coupling Regime via Cavity Mode Tuning

Vibrational Coupling of Water from Weak to Ultrastrong Coupling Regime via Cavity Mode Tuning

Chemistry under Vibrational Strong Coupling

Polariton relaxation under vibrational strong coupling: Comparing cavity molecular dynamics simulations against Fermi's golden rule rate

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