Polariton ring currents and circular dichroism of Mg-porphyrin in a chiral cavity

Sun, Shichao; Gu, Bing; Mukamel, Shaul

doi:10.1039/d1sc04341b

Cited by 25 publications

(32 citation statements)

References 63 publications

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“…The relatively narrow width of the Soret peak in the UV–vis absorption spectra of many porphyrin molecules makes them excellent candidates for cavity polariton formation, as demonstrated by several previous studies. − When coupled with appropriate measurements approaches, these narrow peak widths enable rigorous analysis of the ultrafast dynamics imprinted onto linear polariton spectra directly . Furthermore, the complex coupling between the B and Q states of some highly symmetric metalloporphyrins leads to the possible formation of polariton-like states whose energies lie far away from those resonator photons .…”

Section: Introductionmentioning

confidence: 93%

Cavity Polaritons Formed from Spatially Separated Quasi-degenerate Porphyrin Excitons: Structural Modulations of Bright and Dark State Energies and Compositions

Avramenko

Rury

2022

J. Phys. Chem. C

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In this study, we assess the properties of cavity polaritons formed from the strong coupling of photons to nearly degenerate molecular excitons located in separate layers of multilayer Fabry−Perot resonators. By embedding copper(II) tetraphenylporphyrin (CuTPP) and free base tetraphenylporphyrin (H 2 TPP) in separate layers of the intracavity region, we present evidence of cavity polariton formation using angularly resolved transmission spectra. Multichromophore models enable our characterization of the polariton states consistent with our experimental results. The results show the existence of a middle polariton state whose photonic content does exceed 5% for any fabricated sample, which makes these states spectroscopically dark. We use models of the excited state potential energy surfaces of each porphyrin molecular species to compute and characterize modulations of multipolariton energies due to atomic motions along the reorganizational coordinate of each chromophore. These calculations indicate modulations of each molecule's structure lead to changes in the composition and energy of the multipolariton states. In particular, by modulating the structure of H 2 TPP, which possesses a lower energy Soret transition, we can drive excitonic resonances that cause the photonic content of the MP state to oscillate between zero and nonzero values. Our results and analysis suggest multipolariton formation from quasi-degenerate molecular excitons could provide means to optoelectronic devices such as THz-rate light modulators useful for classical and quantum information processing protocols.

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Section: Introductionmentioning

confidence: 93%

Cavity Polaritons Formed from Spatially Separated Quasi-degenerate Porphyrin Excitons: Structural Modulations of Bright and Dark State Energies and Compositions

Avramenko

Rury

2022

J. Phys. Chem. C

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“…2b) 35,36 . In the absence of a magnetic field, the two excited states are degenerate and the energy difference between the ground and excited states is ω e = 3.81eV 37 . The transition dipole moments for transitions from |G to |+ mol and…”

Section: Modelmentioning

confidence: 99%

Molecular and solid-state topological polaritons induced by population imbalance

Pannir-Sivajothi¹,

Stern²,

Yuen-Zhou³

2023

Preprint

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Strong coupling between electronic excitations in materials and photon modes results in the formation of polaritons, which display larger nonlinearities than their photonic counterparts due to their material component. We theoretically investigate how to optically control the topological properties of molecular and solid-state exciton-polariton systems by exploiting one such nonlinearity: saturation of electronic transitions. We demonstrate modification of the Berry curvature of three different materials when placed within a Fabry-Perot cavity and pumped with circularly polarized light, illustrating the broad applicability of our scheme. Importantly, while optical pumping leads to non-zero Chern invariants, unidirectional edge states do not emerge in our system as the bulkboundary correspondence is not applicable. This work demonstrates a versatile approach to control topological properties of novel optoelectronic materials.

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“…However, for a dense electronic state manifold, it is possible to observe only a single polariton state . Cavity polaritons have been shown to strongly affect the electronic, optical, and chemical properties of molecules and materials, such as increasing the conductivity of organic semiconductors, reversing the selectivity of a ground-state chemical reaction, improving optical nonlinearity, and enabling long-range electronic and vibrational energy transfer. , These findings triggered intense theoretical studies. ,,,− …”

Section: Introductionmentioning

confidence: 99%

Optical Cavity Manipulation and Nonlinear UV Molecular Spectroscopy of Conical Intersections in Pyrazine

Cho

Mukamel

2022

J. Am. Chem. Soc.

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Optical cavities provide a versatile platform for manipulating the excited-state dynamics of molecules via strong light–matter coupling. We employ optical absorption and two-multidimensional electronic spectroscopy simulations to investigate the effect of optical cavity coupling in the nonadiabatic dynamics of photoexcited pyrazine. We observe the emergence of a novel polaritonic conical intersection (PCI) between the electronic dark state and photonic surfaces as the cavity frequency is tuned. The PCI could significantly change the nonadiabatic dynamics of pyrazine by doubling the decay rate constant of the S2 state population. Moreover, the absorption spectrum and excited-state dynamics could be systematically manipulated by tuning the strong light–matter interaction, e.g., the cavity frequency and cavity coupling strength. We propose that a tunable optical cavity–molecule system may provide promising approaches for manipulating the photophysical properties of molecules.

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Polariton ring currents and circular dichroism of Mg-porphyrin in a chiral cavity

Abstract: By placing a Mg-porphyrin molecule in a chiral optical cavity, time reversal symmetry is broken, thus generating polariton ring currents even with linearly polarized light. These currents induce a circular...

Cited by 25 publications

References 63 publications

Cavity Polaritons Formed from Spatially Separated Quasi-degenerate Porphyrin Excitons: Structural Modulations of Bright and Dark State Energies and Compositions

Cavity Polaritons Formed from Spatially Separated Quasi-degenerate Porphyrin Excitons: Structural Modulations of Bright and Dark State Energies and Compositions

Molecular and solid-state topological polaritons induced by population imbalance

Optical Cavity Manipulation and Nonlinear UV Molecular Spectroscopy of Conical Intersections in Pyrazine

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