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Theory for Cavity-Modified Ground-State Reactivities via Electron-Photon Interactions
Arkajit Mandal1,2, Michael A D Taylor3, Pengfei Huo1,3
1Department of Chemistry, University of Rochester, 120 Trustee Road, Rochester, New York 14627, United States.
The Journal of Physical Chemistry. A
|July 27, 2023
Summary
We present a theory showing how optical cavities modify molecular reactivity via quantum light-matter interactions. This approach alters ground-state potentials, enabling control over chemical reactions through cavity coupling.
Area of Science:
- Quantum Chemistry
- Physical Chemistry
- Spectroscopy
Background:
- Light-matter interactions are crucial in chemistry.
- Optical cavities can influence molecular properties.
- Understanding quantum effects in modified environments is key.
Purpose of the Study:
- To develop a simple theory for light-matter interactions modifying molecular reactivity.
- To explain how coupling molecules to optical cavities affects ground-state chemical reactions.
- To provide a theoretical framework for controlling reactivity via quantum effects.
Main Methods:
- Developed a theory based on polarized Fock states representation.
- Analyzed changes in ground-state potential via diabatic electronic couplings.
- Investigated a proton-transfer model system under varying cavity frequencies.
Main Results:
- Demonstrated modification of ground-state potential through light-matter interactions.
- Showed that ground-state barrier height can be tuned by cavity frequency.
- Identified polaritonic eigenstates as Mulliken-Hush diabatic states in the deep strong coupling limit.
Conclusions:
- The theory provides an intuitive explanation for cavity-induced reactivity changes.
- Ground-state reactivity can be controlled by manipulating light-matter coupling.
- This framework aids in understanding and designing quantum-enhanced chemical processes.
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