Abstract
We present an ab initio correlated approach to study molecules that interact strongly with quantum fields in an optical cavity. Quantum electrodynamics coupled cluster theory provides a nonperturbative description of cavity-induced effects in ground and excited states. Using this theory, we show how quantum fields can be used to manipulate charge transfer and photochemical properties of molecules. We propose a strategy to lift electronic degeneracies and induce modifications in the ground-state potential energy surface close to a conical intersection.
- Received 9 May 2020
- Revised 6 September 2020
- Accepted 14 October 2020
DOI:https://doi.org/10.1103/PhysRevX.10.041043
Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article’s title, journal citation, and DOI.
Published by the American Physical Society
Physics Subject Headings (PhySH)
Viewpoint
ViewpointA Comprehensive Framework for Modeling Molecular Polaritons
Published 2 December 2020
Predicting interactions between molecules and photons is now possible with a new model that combines quantum electrodynamics and a widely used formalism from quantum chemistry.
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Popular Summary
The manipulation of atoms and molecules via light has become a popular technique to design and explore new states of matter. In particular, strong couplings between electromagnetic fields and molecules can lead to particlelike “molecular polaritons,” which have been experimentally shown to have a profound impact on chemical reactions taking place inside optical cavities. To understand the fundamental processes taking place in these systems, theoretical simulations are essential. To this end, we have developed an accurate quantum-mechanical method to investigate molecular polaritons.
Our theoretical description extends coupled cluster theory—a well-established technique for applying principles of quantum physics to predict chemical interactions—to incorporate quantum electrodynamics. Using this method, we show that quantum fields can manipulate charge-transfer excitations and the photochemistry of molecules. The methodology paves the way for novel strategies to control molecular chemistry. In particular, we show that an optical cavity can change the ground- and excited-state properties of molecules as well as the interactions between those states.
The development of coupled cluster methods for strong light-matter coupling will form the basis for future studies in cavity quantum electrodynamics, providing methodologies with quantitative accuracy in chemical predictions.
