Control of Photoswitching Kinetics with Strong Light–Matter Coupling in a Cavity

Zeng, Hongfei; Pérez-Sánchez, Juan B.; Eckdahl, Christopher T.; Liu, Pufan; Chang, Woo Je; Weiss, Emily A.; Kalow, Julia A.; Yuen-Zhou, Joel; Stern, Nathaniel P.

doi:10.1021/jacs.3c04254

Cited by 23 publications

(14 citation statements)

References 39 publications

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“…However, these experiments may benefit from similar re-examinations to verify that changes in reaction rates indeed to strong coupling rather than the inadvertent enhanced absorption of photons critical for the photochemical process, or some other effect. Our findings may provide an explanation for the recent work of Zeng et al, [57] who also report that SPI/MC photoisomerization is suppressed when the strong coupling condition is met, but find that fulgicide photoswitching is accelerated under strong coupling. This might perhaps be explained by the two processes being promoted by absorption of different energy light, resulting in cavity-modified photochemistry being predicted by different absorption profiles.…”

Section: Discussionsupporting

confidence: 80%

Non‐Polaritonic Effects in Cavity‐Modified Photochemistry

Thomas,

Tan,

Kravets

et al. 2023

Advanced Materials

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Strong coupling of molecules to vacuum fields is widely reported to lead to modified chemical properties such as reaction rates. However, some recent attempts to reproduce infrared strong coupling results have not been successful, suggesting that factors other than strong coupling may sometimes be involved. In the first vacuum‐modified chemistry experiment, changes to a molecular photoisomerization process in the ultraviolet‐visible spectral range are attributed to strong coupling of the molecules to visible light. Here, this process is re‐examined, finding significant variations in photoisomerization rates consistent with the original work. However, there is no evidence that these changes need to be attributed to strong coupling. Instead, it is suggested that the photoisomerization rates involved are most strongly influenced by the absorption of ultraviolet radiation in the cavity. These results indicate that care must be taken to rule out non‐polaritonic effects before invoking strong coupling to explain any changes of properties arising in cavity‐based experiments.

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Section: Discussionsupporting

confidence: 80%

Non‐Polaritonic Effects in Cavity‐Modified Photochemistry

Thomas,

Tan,

Kravets

et al. 2023

Advanced Materials

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“…However, within this explanation, the role of dark reservoir modes was not directly considered. This work has been reproduced recently 174 by a different group independently.…”

Section: Molecular Reactions Modified By Strong Couplingmentioning

confidence: 83%

Molecular Polaritons for Chemistry, Photonics and Quantum Technologies

Xiang,

Xiong

2024

Chem. Rev.

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Molecular polaritons are quasiparticles resulting from the hybridization between molecular and photonic modes. These composite entities, bearing characteristics inherited from both constituents, exhibit modified energy levels and wave functions, thereby capturing the attention of chemists in the past decade. The potential to modify chemical reactions has spurred many investigations, alongside efforts to enhance and manipulate optical responses for photonic and quantum applications. This Review centers on the experimental advances in this burgeoning field. Commencing with an introduction of the fundamentals, including theoretical foundations and various cavity architectures, we discuss outcomes of polariton-modified chemical reactions. Furthermore, we navigate through the ongoing debates and uncertainties surrounding the underpinning mechanism of this innovative method of controlling chemistry. Emphasis is placed on gaining a comprehensive understanding of the energy dynamics of molecular polaritons, in particular, vibrational molecular polaritons�a pivotal facet in steering chemical reactions. Additionally, we discuss the unique capability of coherent twodimensional spectroscopy to dissect polariton and dark mode dynamics, offering insights into the critical components within the cavity that alter chemical reactions. We further expand to the potential utility of molecular polaritons in quantum applications as well as precise manipulation of molecular and photonic polarizations, notably in the context of chiral phenomena. This discussion aspires to ignite deeper curiosity and engagement in revealing the physics underpinning polariton-modified molecular properties, and a broad fascination with harnessing photonic environments to control chemistry.

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“…A pioneering study by Ebbesen and co-workers showed that the rate of the ring-opening photoisomerization of spiropyran (SP) into merocyanine (MC) was slowed by approximately an order of magnitude in cavities that were tuned to be resonant with the product state . Recent studies reproduce this empirical finding, , though one study suggests that the effect is nonpolaritonic . In this work, we study the opposite reaction from MC to SP, with the reactant (rather than the product) strongly coupled to the cavity mode.…”

Section: Introductionmentioning

confidence: 99%

“…Although this study shows a suppression of the photoisomerization yield, strong coupling enables lowering of the photon energy required to drive photoisomerization. Finally, recent work by Stern and co-workers shows that the photoswitching kinetics of fulgides is accelerated by cavity strong coupling.…”

Section: Introductionmentioning

confidence: 99%

Controlling Molecular Photoisomerization in Photonic Cavities through Polariton Funneling

Lee,

Melton,

et al. 2024

J. Am. Chem. Soc.

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Strong coupling between photonic modes and molecular electronic excitations, creating hybrid light-matter states called polaritons, is an attractive avenue for controlling chemical reactions. Nevertheless, experimental demonstrations of polaritonmodified chemical reactions remain sparse. Here, we demonstrate modified photoisomerization kinetics of merocyanine and diarylethene by coupling the reactant's optical transition with photonic microcavity modes. We leverage broadband Fourier-plane optical microscopy to noninvasively and rapidly monitor photoisomerization within microcavities, enabling systematic investigation of chemical kinetics for different cavity-exciton detunings and photoexcitation conditions. We demonstrate three distinct effects of cavity coupling: first, a renormalization of the photonic density of states, akin to a Purcell effect, leads to enhanced absorption and isomerization rates at certain wavelengths, notably red-shifting the onset of photoisomerization. This effect is present under both strong and weak light-matter couplings. Second, kinetic competition between polariton localization into reactive molecular states and cavity losses leads to a suppression of the photoisomerization yield. Finally, our key result is that in reaction mixtures with multiple reactant isomers, exhibiting partially overlapping optical transitions and distinct isomerization pathways, the cavity resonance can be tuned to funnel photoexcitations into specific reactant isomers. Thus, upon decoherence, polaritons localize into a chosen isomer, selectively triggering the latter's photoisomerization despite initially being delocalized across all isomers. This result suggests that careful tuning of the cavity resonance is a promising avenue to steer chemical reactions and enhance product selectivity in reaction mixtures.

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Control of Photoswitching Kinetics with Strong Light–Matter Coupling in a Cavity

Cited by 23 publications

References 39 publications

Non‐Polaritonic Effects in Cavity‐Modified Photochemistry

Non‐Polaritonic Effects in Cavity‐Modified Photochemistry

Molecular Polaritons for Chemistry, Photonics and Quantum Technologies

Controlling Molecular Photoisomerization in Photonic Cavities through Polariton Funneling

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