Recent Progress in Vibropolaritonic Chemistry

Hirai, Kenji; Hutchison, James A.; Uji‐i, Hiroshi

doi:10.1002/cplu.202000411

Cited by 106 publications

(148 citation statements)

References 53 publications

(82 reference statements)

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“…Chemistry under strong coupling has received much attention since the first demonstration of a modified chemical landscape [7–34] . Recently, we reported that vibrational symmetry plays a key role in modifying the charge‐transfer complexation equilibrium between I 2 and mesitylene under vibrational strong coupling (VSC) [12] .…”

Section: Figurementioning

confidence: 99%

Modifying Woodward–Hoffmann Stereoselectivity Under Vibrational Strong Coupling

Nagarajan

Patrahau

et al. 2021

Angew Chem Int Ed

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Vibrational strong coupling (VSC) has recently been shown to change the rate and chemoselectivity of ground‐state chemical reactions via the formation of light–matter hybrid polaritonic states. However, the observation that vibrational‐mode symmetry has a large influence on charge‐transfer reactions under VSC suggests that symmetry considerations could be used to control other types of chemical selectivity through VSC. Here, we show that VSC influences the stereoselectivity of the thermal electrocyclic ring opening of a cyclobutene derivative, a reaction which follows the Woodward–Hoffmann rules. The direction of the change in stereoselectivity depends on the vibrational mode that is coupled, as do changes in rate and reaction thermodynamics. These results on pericyclic reactions confirm that symmetry plays a key role in chemistry under VSC.

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Section: Figurementioning

confidence: 99%

Modifying Woodward–Hoffmann Stereoselectivity Under Vibrational Strong Coupling

Nagarajan

Patrahau

et al. 2021

Angew Chem Int Ed

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“…There were very few attempts from the experimental side to understand the role of VSC on chemical reactions. 36 Hirai et al, shown that VSC can control a cycloaddition reaction. 37 Thermodynamic experiments suggest that the polarity of the C=O group got affected under VSC that decelerated the reaction rate.…”

Section: Cavity Catalysismentioning

confidence: 99%

Cavity Catalysis: Modifying Linear Free-energy Relationship under Cooperative Vibrational Strong Coupling

George

Lather

Ahammad

et al. 2021

Preprint

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Recent understanding of light-matter strong coupling brought a new niche in molecular-level control of chemical reactions. Vibrational strong coupling is unique in this category that overcomes the issue associated with coherent chemistry. Here, a vibrational transition is coupled to a standing wave of electromagnetic field, result in strong interaction, generating vibro-polaritonic states. This process reshuffles the entire energy-reaction coordinate. The chemical reaction rate can be boosted, stirred, or decelerated with this unconventional tool. Here, we used the idea of cooperative vibrational strong coupling of solute and solvent molecules to enhance the chemical reaction rate. This process is called cavity catalysis. Different derivatives of p-nitrophenyl benzoate (solute) and isopropyl acetate (solvent) are cooperatively coupled to an infrared Fabry-Perot cavity. The apparent reaction rates are increased by more than six times at the ON resonance condition, and the rate enhancement follows the lineshape of the vibrational envelope. Very interestingly, strong coupled system doesn't follow a linear free-energy relationship. The nonlinear rate enhancement can be due to the reshuffling of energy distribution between the substituents and the reaction center. Thermodynamic parameters suggest an entropy-driven process for the coupled molecules. The free energy of activation decreased by 2-5 kJ/mol, suggesting a clear role of vibrational strong coupling in catalyzing the reaction. Here, the enthalpy of the system compensates for the entropy by preserving the isokinetic relationship. These findings will help further understanding of chemical reaction control in polariton chemistry. TOC

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“…Polariton Chemistry is an emerging field [1][2][3][4][5] that provides opportunities for new chemical reactivities or selectivities by coupling molecular systems to quantized radiation fields inside an optical cavity. By hybridizing vibrational excitations of the molecule with the photonic excitation of the radiation inside the cavity, new light-matter entangled states, so-called the polariton states are generated.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, it has been demonstrated that it is possible to suppress [6][7][8][9][10] or enhance 11,12 ground state chemical reactivities by placing an ensemble of molecules in an optical micro-cavity through the resonant coupling between the cavity and vibrational degrees of freedom (DOF) of the molecules. This so-called vibrational strong coupling (VSC) regime 5 operates in the absence of any light source, 7,8 and was hypothesized to utilize the hybridization of a vibrational transition of a molecule and the zero-point energy fluctuations of a cavity mode. 7,8 In a recent ground-breaking experiment, Ebbesen and co-workers 7 have demonstrated that the cavity can selectively slow down a particular reaction among competing reaction pathways, and revert the reactive selectivities.…”

Section: Introductionmentioning

confidence: 99%

Mode-Selective Chemistry through Polaritonic Vibrational Strong Coupling

Li¹,

Mandal²,

Huo³

2021

Preprint

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Recent experiments have demonstrated remarkable mode-selective reactivities by coupling molecular vibrations with vacuum fluctuations inside an optical cavity. The fundamental mechanism behind such effects, on the other hand, remains elusive. In this work, we theoretically demonstrate the basic principle of how cavity photon frequency can be tuned to achieve mode-selective reactivities. We find that the non-Markovian nature of the radiation mode leads to a cavity frequency-dependent dynamical caging effect of a reaction coordinate, resulting in a suppression of the rate constant. In the presence of multiple competitive reactions, it is possible to preferentially cage a reaction coordinate when the barrier frequencies for competing reaction paths are different. Our theoretical results illustrate the cavity-induced mode-selective chemistry through polaritonic vibrational-strong couplings, revealing the fundamental mechanism for changing chemical selectivities through cavity quantum electrodynamics.

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Recent Progress in Vibropolaritonic Chemistry

Cited by 106 publications

References 53 publications

Modifying Woodward–Hoffmann Stereoselectivity Under Vibrational Strong Coupling

Modifying Woodward–Hoffmann Stereoselectivity Under Vibrational Strong Coupling

Cavity Catalysis: Modifying Linear Free-energy Relationship under Cooperative Vibrational Strong Coupling

Mode-Selective Chemistry through Polaritonic Vibrational Strong Coupling

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