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Vibrational and electronic strong coupling of light with molecular excitations has shown promise for modifying chemical reaction rates. However, the Tavis–Cummings model often used to model such polaritonic chemistry considers only a single discrete cavity mode coupled with the molecular modes, while experimental systems generally consist of a larger number of molecules in cavities with a continuum of modes. Here, we model the polaritonic effects of multimode cavities of arbitrary dimensions and filled with a large number of molecules. We obtain the dependence of the effects on the dimensionality of the cavity, the molecular oscillator strength, and molecular concentration. Combining our model with the transition state theory, we show that polaritonic effects can be altered by a few orders of magnitude compared to including only a single cavity mode, and that the effect is stronger with a larger molecular dipole moment and molecular concentration. However, the change remains negligibly small for realistic chemical systems due to the large number of dark states.
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Resolving ambiguities of the mode truncation in cavity quantum electrodynamics
This work provides the fundamental theoretical framework for few-mode cavity quantum electrodynamics by resolving the gauge ambiguities between the Coulomb gauge and the dipole gauge Hamiltonians under the photonic mode truncation. We first propose a general framework to resolve ambiguities for an arbitrary truncation in a given gauge. Then, we specifically consider the case of mode truncation, deriving gauge invariant expressions for both the Coulomb and dipole gauge Hamiltonians that naturally reduce to the commonly used single-mode Hamiltonians when considering a single-mode truncation. We finally provide the analytical and numerical results of both atomic and molecular model systems coupled to the cavity to demonstrate the validity of our theory.
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- Award ID(s):
- 2124398
- PAR ID:
- 10368704
- Publisher / Repository:
- Optical Society of America
- Date Published:
- Journal Name:
- Optics Letters
- Volume:
- 47
- Issue:
- 6
- ISSN:
- 0146-9592; OPLEDP
- Format(s):
- Medium: X Size: Article No. 1446
- Size(s):
- Article No. 1446
- Sponsoring Org:
- National Science Foundation
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