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• W4385968849 abstract "Explanation for the modification of rates and mechanism of reactions carried out in optical cavities still eludes us. Several studies indicate that the cavity-mediated changes in the nature of vibrational energy flow within a molecule may play a significant role. Here, we study a model polaritonic system, proposed and analyzed earlier by Fischer et al., J. Chem. Phys. 156, 154305 (2022), comprising a one-dimensional isomerization mode coupled to a single photon mode in a lossless cavity. We show that the isomerization probability in the presence of virtual photons, for specific cavity-system coupling strengths and cavity frequencies, can exhibit suppression or enhancement for different choices of the initial reactant vibropolariton wavepacket. We observe a qualitative agreement between the classical and quantum average isomerization probabilities in the virtual photon case. A significant part of the effects due to coupling to the cavity can be rationalized in terms of a chaos-order-chaos transition of the classical phase space and the phase space localization nature of the polariton states that dominantly participate in the quantum isomerization dynamics. On the other hand, for initial states with zero photons (i.e., a dark cavity), the isomerization probability is suppressed when the cavity frequency is tuned near to the fundamental frequency of the reactive mode. The classical-quantum correspondence in the zero photon case is unsatisfactory. In this simple model, we find that the suppression or enhancement of isomerization arises due to the interplay between cavity-system energy flow dynamics and quantum tunneling." @default.
• W4385968849 created "2023-08-19" @default.
• W4385968849 creator A5073278618 @default.
• W4385968849 creator A5082811518 @default.
• W4385968849 date "2023-08-18" @default.
• W4385968849 modified "2023-10-06" @default.
• W4385968849 title "Phase space perspective on a model for isomerization in an optical cavity" @default.
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• W4385968849 doi "https://doi.org/10.1063/5.0160586" @default.
• W4385968849 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/37594071" @default.
• W4385968849 hasPublicationYear "2023" @default.
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