Negligible rate enhancement from reported cooperative vibrational strong coupling catalysis

Xiong, Wei; Wiesehan, Garret Douglas

doi:10.1063/5.0077549

Cited by 69 publications

(73 citation statements)

References 53 publications

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“…In the conventional approach concentrating on the cavity induced modification of the individual reaction rates within the transition state theory, it is found that all the polaritonic effects should disappear when the number of molecules forming the polariton is increased [20][21][22][23]. Furthermore, very recently, there have been reports of failed replication experiments [24,25], adding to the confusion.…”

mentioning

confidence: 99%

Cavity-induced bifurcation in classical rate theory

Kansanen¹,

Heikkilä²

2022

Preprint

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We show how coupling an ensemble of bistable systems to a common cavity field affects the collective stochastic behavior of this ensemble. In particular, the cavity provides an effective interaction between the systems, and parametrically modifies the transition rates between the metastable states. We predict that for a coupling strength exceeding a certain threshold, the cavity induces a spontaneous symmetry breaking where the stationary states of the bistable system bifurcate and the systems coalesce preferentially in one of the states. The effect crucially depends on the distribution of system-cavity coupling strengths. In the case of alternating signs of the couplings, the bifurcation shows up as a phase separation. Our results are of particular relevance in polaritonic chemistry where the presence of a cavity has been suggested to affect chemical reactions.

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confidence: 99%

Cavity-induced bifurcation in classical rate theory

Kansanen¹,

Heikkilä²

2022

Preprint

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“…. (11) In Eq. 10, δ L and δ R are the average (dimensionless) energy loss from the unstable mode when the system returns to the barrier, associated with the left and right wells, respectively, and can be obtained from [39]…”

Section: B Rate Theorymentioning

confidence: 99%

“…A series of recent experiments [1][2][3][4][5][6][7][8] have demonstrated that chemical kinetics can be enhanced [4,6,8] or suppressed [1,5], molecular bonds can be selectively broken [2], and selective crystallization can be achieved [9] via the formation of vibrational polaritons. On the other hand, several studies [10,11] have also reported possible discrepancies or inconsistencies in the interpretation of experiment purporting sizable kinetic effects. Thus, a rigorous theoretical understanding of the range of possible cavity-induced modifications to chemical kinetics is actively sought.…”

Section: Introductionmentioning

confidence: 99%

Resonant Cavity Modification of Ground State Chemical Kinetics

Lindoy,

Mandal,

Reichman

2022

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Recent experiments have suggested that ground state chemical kinetics can be suppressed or enhanced by coupling the vibrational degrees of freedom of a molecular system with a radiation mode inside an optical cavity. Experiments show that the chemical rate is strongly modified when the photon frequency is close to characteristic vibrational frequencies. The origin of this remarkable effect remains unknown. In this work, we develop an analytical rate theory for cavity-modified ground state chemical kinetics based on the Pollak-Grabert-Hänggi rate theory. Unlike previous work, our theory covers the complete range of solvent friction values, from the energy-diffusion limited to the spatial-diffusion limited regimes. We show that the chemical reaction rate can either be enhanced or suppressed depending on the bath friction; when bath friction is weak chemical kinetics is enhanced as opposed to the case of strong bath friction, where chemical kinetics is suppressed. Further, we show that the photon frequency at which maximum modification of chemical rate is achieved is close to the reactant well, and hence resonant rate modification occurs. In the strong friction limit the resonant photon frequency is instead close to the barrier frequency, as obtained using the Grote-Hynes rate theory. Finally, we observe that the rate changes (as a function of photon frequency) are much sharper and more sizable in the weak friction limit than in the strong friction limit, and become increasingly sharp with decreasing well frequency.

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“…A possible way to circumvent these two obstacles is to tune the frequencies of an optical cavity to selectively alter the ground state chemical reactivity of molecules, which was demonstrated recently experimentally. [1][2][3] This research avenue has attracted many experimental, [4][5][6][7] computational, [8][9][10][11][12][13][14][15][16] and theoretical [17][18][19][20] investigations in recent years as which reactions can be manipulated by optical cavities and the underlying mechanism of how cavities can modify chemical reactivity are still an open questions. [21][22][23] In this work, we study the reaction rate inside an optical cavity by developing a non-Markovian dynamical model.…”

Section: Introductionmentioning

confidence: 99%

Chemical reactions in imperfect cavities: enhancement, suppression, and resonance

Philbin¹,

Wang²,

Narang³

et al. 2022

Preprint

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The use of optical cavities to control chemical reactions has been of great interest recently, following demonstrations of enhancement, suppression, and negligible effects on chemical reaction rates depending on the specific reaction and cavity frequency. In this work, we study the reaction rate inside imperfect cavities, where we introduce a broadening parameter in the spectral density to mimic Fabry-Pérot cavities. We investigate cavity modifications to reaction rates using non-Markovian Langevin dynamics with frictional and random forces to account for the presence of imperfect optical cavities. We demonstrate that in the regime of weak solvent and cavity friction, the cavity can enhance chemical reaction rates. On the other hand, in the high friction regime, cavities can suppress chemical reactions. Furthermore, we find that the broadening of the cavity spectral density gives rise to blue shifts of the resonance conditions and, surprisingly, increases the sharpness of the resonance effect.

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Negligible rate enhancement from reported cooperative vibrational strong coupling catalysis

Cited by 69 publications

References 53 publications

Cavity-induced bifurcation in classical rate theory

Cavity-induced bifurcation in classical rate theory

Resonant Cavity Modification of Ground State Chemical Kinetics

Chemical reactions in imperfect cavities: enhancement, suppression, and resonance

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