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.5 MoreReceived 9 May 2020Revised 6 September 2020Accepted 14 October 2020DOI:https://doi.org/10.1103/PhysRevX.10.041043Published 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 SocietyPhysics Subject Headings (PhySH)Research AreasCavity quantum electrodynamicsChemical Physics & Physical ChemistryElectronic structureElectronic transitionsPolaritonsTechniquesAb initio calculationsCoupled clusterHartree-Fock methodsAtomic, Molecular & Optical
Highlights
Manipulation by strong electron-photon coupling [1] and laser fields [2,3,4] is becoming a popular technique to design and explore new states of matter
Quantum electrodynamics coupled cluster theory provides a nonperturbative description of cavity-induced effects in ground and excited states
Ebbesen and co-workers have found that strong coupling to vibrational excited states in molecules can inhibit [13,14,15], catalyze [16,17], and induce selective change in the reactive path of a chemical reaction [18]
Summary
Manipulation by strong electron-photon coupling [1] and laser fields [2,3,4] is becoming a popular technique to design and explore new states of matter. Ebbesen and co-workers have found that strong coupling to vibrational excited states in molecules can inhibit [13,14,15], catalyze [16,17], and induce selective change in the reactive path of a chemical reaction [18] These experiments use an optical cavity, the simplest device in which entanglement between matter and light can be observed. In an optical cavity (see Fig. 1), the quantized electromagnetic field interacts with the molecular system, producing new hybrid light-matter states called polaritons [19]. Coupled cluster theory is one of the most successful methods for treating electron correlation in both ground and excited states of molecular systems [36,37]. These results pave the way for novel strategies to control photochemical reaction paths
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