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Vibrational Polaritons in Disordered Molecular Ensembles.

ABSTRACT: Disorder is an intrinsic attribute of any realistic molecular system. It is known to lead to localization, which hampers efficient transport. It was recently proposed that in molecular ensembles strongly coupled to photonic cavities, moderate disorder leads to delocalization and increases of the transport and chemical reaction rates. Vibrational polaritons involve molecular vibrations hybridized with an infrared cavity. When the coupling strength largely exceeds the molecular inhomogeneity, polaritons are unaffected by disorder. However, in many experiments, such a homogeneous limit does not apply. We investigated vibrational polaritons involving molecular ensembles with systematically modified disorder. Counterintuitively, moderate disorder leads to an increase in Rabi splitting and the modification of the polariton bandwidths. Experimental spectroscopic data agree with a Tavis-Cummings-like model that suggests enhanced delocalization of the reservoir states occurs via the admixture of the cavity mode. Our results provide new insights into the paradigm of disorder-induced cavity-assisted delocalization in molecular polaritons.

SUBMITTER: Cohn B

PROVIDER: S-EPMC9465717 | biostudies-literature | 2022 Sep

REPOSITORIES: biostudies-literature

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Vibrational Polaritons in Disordered Molecular Ensembles.

Cohn Bar B Sufrin Shmuel S Basu Arghyadeep A Chuntonov Lev L

The journal of physical chemistry letters 20220831 35

Disorder is an intrinsic attribute of any realistic molecular system. It is known to lead to localization, which hampers efficient transport. It was recently proposed that in molecular ensembles strongly coupled to photonic cavities, moderate disorder leads to delocalization and increases of the transport and chemical reaction rates. Vibrational polaritons involve molecular vibrations hybridized with an infrared cavity. When the coupling strength largely exceeds the molecular inhomogeneity, pola ...[more]

PMID: 36043884

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Project description:Vibrational polaritons, which have been primarily studied in Fabry-Pérot cavities with a large number of molecules (N ∼ 106-1010) coupled to the resonator mode, exhibit various experimentally observed effects on chemical reactions. However, the exact mechanism is elusively understood from the theoretical side, as the large number of molecules involved in an experimental strong coupling condition cannot be represented completely in simulations. This discrepancy between theory and experiment arises from computational descriptions of polariton systems typically being limited to only a few molecules, thus failing to represent the experimental conditions adequately. To address this mismatch, we used surface phonon polariton (SPhP) resonators as an alternative platform for vibrational strong coupling. SPhPs exhibit strong electromagnetic confinement on the surface and thus allow for coupling to a small number of molecules. As a result, this platform can enhance nonlinearity and slow down relaxation to the dark modes. In this study, we fabricated a pillar-shaped quartz resonator and then coated it with a thin layer of cobalt phthalocyanine (CoPc). By employing scattering-type scanning near-field optical microscopy (s-SNOM), we spatially investigated the dependency of vibrational strong coupling on the spatially varying electromagnetic field strength and demonstrated strong coupling with 38,000 molecules only-reaching to the small N limit. Through s-SNOM analysis, we found that strong coupling was observed primarily on the edge of the quartz pillar and the apex of the s-SNOM tip, where the maximum field enhancement occurs. In contrast, a weak resonance signal and lack of coupling were observed closer to the center of the pillar. This work demonstrates the importance of spatially resolved polariton systems in nanophotonic platforms and lays a foundation to explore polariton chemistry and chemical dynamics at the small N limit-one step closer to reconcile with high-level quantum calculations.

Dataset Information

Vibrational Polaritons in Disordered Molecular Ensembles.

Publications

Vibrational Polaritons in Disordered Molecular Ensembles.

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