ArticleThe journal of physical chemistry letters2020
Chemistry in Quantum Cavities: Exact Results, the Impact of Thermal Velocities, and Modified Dissociation.
Article in The journal of physical chemistry letters, 2020. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 10 papers.
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Who cites it
10 citing papers in PubMed.
- Quantum-Electrodynamical Time-Dependent Density Functional Theory Description of Molecules in Optical Cavities.Journal of chemical theory and computation · 2026Article
- Collectively-Modified Intermolecular Electron Correlations: The Connection of Polaritonic Chemistry and Spin Glass Physics.Chemical reviews · 2026Review
- Cavity-mediated electron-electron interactions: Renormalizing Dirac states in graphene.Science advances · 2025Article
- Unraveling a Cavity-Induced Molecular Polarization Mechanism from Collective Vibrational Strong Coupling.The journal of physical chemistry letters · 2024Article
- Numerically Exact Solution for a Real Polaritonic System under Vibrational Strong Coupling in Thermodynamic Equilibrium: Loss of Light-Matter Entanglement and Enhanced Fluctuations.Journal of chemical theory and computation · 2023Article
- Understanding Polaritonic Chemistry from Ab Initio Quantum Electrodynamics.Chemical reviews · 2023Review
- Manipulating hydrogen bond dissociation rates and mechanisms in water dimer through vibrational strong coupling.Nature communications · 2023Article
- Frequency-Dependent Sternheimer Linear-Response Formalism for Strongly Coupled Light-Matter Systems.Journal of chemical theory and computation · 2022Article
- Polaritonic Chemistry: Collective Strong Coupling Implies Strong Local Modification of Chemical Properties.The journal of physical chemistry letters · 2021Article
- Virial Relations for Electrons Coupled to Quantum Field Modes.Journal of chemical theory and computation · 2020Article
Corrections and comments
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Authors and funding
4 authors.
Funding
No grant is acknowledged in the PubMed record.
Abstract
In recent years tremendous progress in the field of light-matter interactions has unveiled that strong coupling to the modes of an optical cavity can alter chemistry even at room temperature. Despite these impressive advances, many fundamental questions of chemistry in cavities remain unanswered. This is also due to a lack of exact results that can be used to validate and benchmark approximate approaches. In this work we provide such reference calculations from exact diagonalization of the Pauli-Fierz Hamiltonian in the long-wavelength limit with an effective cavity mode. This allows us to investigate the reliability of the ubiquitous Jaynes-Cummings model not only for electronic but also for the case of ro-vibrational transitions. We demonstrate how the commonly ignored thermal velocity of charged molecular systems can influence chemical properties while leaving the spectra invariant. Furthermore, we show the emergence of new bound polaritonic states beyond the dissociation energy limit.
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