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  Modification of excitation and charge transfer in cavity quantum-electrodynamical chemistry

Schäfer, C., Ruggenthaler, M., Appel, H., & Rubio, A. (2019). Modification of excitation and charge transfer in cavity quantum-electrodynamical chemistry. Proceedings of the National Academy of Sciences of the United States of America, 116(11), 4883-4892. doi:10.1073/pnas.1814178116.

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Item Permalink: http://hdl.handle.net/21.11116/0000-0002-AB84-8 Version Permalink: http://hdl.handle.net/21.11116/0000-0003-A36B-D
Genre: Journal Article

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https://dx.doi.org/10.1073/pnas.1814178116 (Publisher version)
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 Creators:
Schäfer, C.1, 2, Author              
Ruggenthaler, M.1, 2, Author              
Appel, H.1, 2, Author              
Rubio, A.1, 2, Author              
Affiliations:
1Theory Group, Theory Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society, ou_2266715              
2The Center for Free-Electron Laser Science, ou_persistent22              

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Free keywords: QED chemistry; correlated chemistry; long-range energy transfer; stronglight–matter interaction; cavity QED
 Abstract: 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.

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Language(s): eng - English
 Dates: 2018-08-162018-12-122019-02-072019-03-12
 Publication Status: Published in print
 Pages: 10
 Publishing info: -
 Table of Contents: -
 Rev. Method: Peer
 Identifiers: DOI: 10.1073/pnas.1814178116
 Degree: -

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Project name : This work was supported by European Research Council Grant ERC-2015-AdG-694097 and partially supported by Federal Ministry of Education and Research Grant RouTe-13N14839.
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Title: Proceedings of the National Academy of Sciences of the United States of America
  Other : Proc. Acad. Sci. USA
  Other : Proc. Acad. Sci. U.S.A.
  Other : Proceedings of the National Academy of Sciences of the USA
  Abbreviation : PNAS
Source Genre: Journal
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Publ. Info: Washington, D.C. : National Academy of Sciences
Pages: 10 Volume / Issue: 116 (11) Sequence Number: - Start / End Page: 4883 - 4892 Identifier: ISSN: 0027-8424
CoNE: https://pure.mpg.de/cone/journals/resource/954925427230