Modification of excitation and charge transfer in cavity quantum-electrodynamical chemistry.
QED chemistry
cavity QED
correlated chemistry
long-range energy transfer
strong light–matter interaction
Journal
Proceedings of the National Academy of Sciences of the United States of America
ISSN: 1091-6490
Titre abrégé: Proc Natl Acad Sci U S A
Pays: United States
ID NLM: 7505876
Informations de publication
Date de publication:
12 03 2019
12 03 2019
Historique:
pubmed:
9
2
2019
medline:
9
2
2019
entrez:
9
2
2019
Statut:
ppublish
Résumé
Energy transfer in terms of excitation or charge is one of the most basic processes in nature, and understanding and controlling them is one of the major challenges of modern quantum chemistry. In this work, we highlight that these processes as well as other chemical properties can be drastically altered by modifying the vacuum fluctuations of the electromagnetic field in a cavity. By using a real-space formulation from first principles that keeps all of the electronic degrees of freedom in the model explicit and simulates changes in the environment by an effective photon mode, we can easily connect to well-known quantum-chemical results such as Dexter charge-transfer and Förster excitation-transfer reactions, taking into account the often-disregarded Coulomb and self-polarization interaction. We find that the photonic degrees of freedom introduce extra electron-electron correlations over large distances and that the coupling to the cavity can drastically alter the characteristic charge-transfer behavior and even selectively improve the efficiency. For excitation transfer, we find that the cavity renders the transfer more efficient, essentially distance-independent, and further different configurations of highest efficiency depending on the coherence times. For strong decoherence (short coherence times), the cavity frequency should be in between the isolated excitations of the donor and acceptor, while for weak decoherence (long coherence times), the cavity should enhance a mode that is close to resonance with either donor or acceptor. Our results highlight that changing the photonic environment can redefine chemical processes, rendering polaritonic chemistry a promising approach toward the control of chemical reactions.
Identifiants
pubmed: 30733295
pii: 1814178116
doi: 10.1073/pnas.1814178116
pmc: PMC6421448
doi:
Types de publication
Journal Article
Research Support, Non-U.S. Gov't
Langues
eng
Pagination
4883-4892Commentaires et corrections
Type : CommentIn
Informations de copyright
Copyright © 2019 the Author(s). Published by PNAS.
Déclaration de conflit d'intérêts
Conflict of interest statement: A.R. and V.S. are both members of the QuantERA RouTe consortium. They are not currently collaborating.
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