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  A perspective on ab initio modeling of polaritonic chemistry: The role of non-equilibrium effects and quantum collectivity

Sidler, D., Ruggenthaler, M., Schäfer, C., Ronca, E., & Rubio, A. (2022). A perspective on ab initio modeling of polaritonic chemistry: The role of non-equilibrium effects and quantum collectivity. The Journal of Chemical Physics, 156(23): 230901. doi:10.1063/5.0094956.

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https://arxiv.org/abs/2108.12244 (Preprint)
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https://doi.org/10.1063/5.0094956 (Publisher version)
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 Creators:
Sidler, D.1, 2, 3, Author           
Ruggenthaler, M.1, 2, 3, Author           
Schäfer, C.1, 2, 3, 4, 5, Author           
Ronca, E.6, Author
Rubio, A.1, 2, 3, 7, 8, Author           
Affiliations:
1Theory Group, Theory Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society, ou_2266715              
2Center for Free-Electron Laser Science, ou_persistent22              
3The Hamburg Center for Ultrafast Imaging, ou_persistent22              
4Department of Physics, Chalmers University of Technology, ou_persistent22              
5Department of Microtechnology and Nanoscience, MC2, Chalmers University of Technology, ou_persistent22              
6Istituto per i Processi Chimico Fisici del CNR (IPCF-CNR), ou_persistent22              
7Center for Computational Quantum Physics, Flatiron Institute, ou_persistent22              
8Nano-Bio Spectroscopy Group, University of the Basque Country (UPV/EHU), ou_persistent22              

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 Abstract: This Perspective provides a brief introduction into the theoretical complexity of polaritonic chemistry, which emerges from the hybrid nature of strongly coupled light–matter states. To tackle this complexity, the importance of ab initio methods is highlighted. Based on those, novel ideas and research avenues are developed with respect to quantum collectivity, as well as for resonance phenomena immanent in reaction rates under vibrational strong coupling. Indeed, fundamental theoretical questions arise about the mesoscopic scale of quantum-collectively coupled molecules when considering the depolarization shift in the interpretation of experimental data. Furthermore, to rationalize recent findings based on quantum electrodynamical density-functional theory (QEDFT), a simple, but computationally efficient, Langevin framework is proposed based on well-established methods from molecular dynamics. It suggests the emergence of cavity-induced non-equilibrium nuclear dynamics, where thermal (stochastic) resonance phenomena could emerge in the absence of external periodic driving. Overall, we believe that the latest ab initio results indeed suggest a paradigmatic shift for ground-state chemical reactions under vibrational strong coupling from the collective quantum interpretation toward a more local, (semi)-classically and non-equilibrium dominated perspective. Finally, various extensions toward a refined description of cavity-modified chemistry are introduced in the context of QEDFT, and future directions of the field are sketched.

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Language(s): eng - English
 Dates: 2022-04-072022-05-122022-06-152022-06-21
 Publication Status: Published in print
 Pages: -
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 Table of Contents: -
 Rev. Type: Peer
 Identifiers: arXiv: 2108.12244
DOI: 10.1063/5.0094956
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Project name : This work was [...] supported by [...] the Cluster of Excellence “CUI: Advanced Imaging 12 of Matter” of the Deutsche Forschungsgemeinschaft (DFG), EXC 2056, project ID 390715994 [...].
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Title: The Journal of Chemical Physics
  Abbreviation : J. Chem. Phys.
Source Genre: Journal
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Publ. Info: Woodbury, N.Y. : American Institute of Physics
Pages: - Volume / Issue: 156 (23) Sequence Number: 230901 Start / End Page: - Identifier: ISSN: 0021-9606
CoNE: https://pure.mpg.de/cone/journals/resource/954922836226