Case studies of the time-dependent potential energy surface for dynamics in cavities

Phillip Martinez; Bart Rosenzweig; Norah M. Hoffmann; Lionel Lacombe; Neepa T. Maitra

doi:10.1063/5.0033386

journal article Jan 06, 2021

Case studies of the time-dependent potential energy surface for dynamics in cavities

Phillip Martinez Bart Rosenzweig Norah M. Hoffmann

Lionel Lacombe

Neepa T. Maitra

The Journal of Chemical Physics Vol. 154 No. 1 · AIP Publishing

View at Publisher Save 10.1063/5.0033386

Abstract

The exact time-dependent potential energy surface driving the nuclear dynamics was recently shown to be a useful tool to understand and interpret the coupling of nuclei, electrons, and photons in cavity settings. Here, we provide a detailed analysis of its structure for exactly solvable systems that model two phenomena: cavity-induced suppression of proton-coupled electron-transfer and its dependence on the initial state, and cavity-induced electronic excitation. We demonstrate the inadequacy of simply using a weighted average of polaritonic surfaces to determine the dynamics. Such a weighted average misses a crucial term that redistributes energy between the nuclear and the polaritonic systems, and this term can in fact become a predominant term in determining the nuclear dynamics when several polaritonic surfaces are involved. Evolving an ensemble of classical trajectories on the exact potential energy surface reproduces the nuclear wavepacket quite accurately, while evolving on the weighted polaritonic surface fails after a short period of time. The implications and prospects for application of mixed quantum-classical methods based on this surface are discussed.

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Cited By

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Understanding Polaritonic Chemistry from Ab Initio Quantum Electrodynamics

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Chemical Reviews

Metrics

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Citations

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References

Details

Published: Jan 06, 2021
Vol/Issue: 154(1)
License: View

Authors

P

Phillip Martinez

Department of Physics and Astronomy, Hunter College of the City University of New York 1 , 695 Park Avenue, New York, New York 10065, USA

B

Bart Rosenzweig

Department of Physics and Astronomy, Hunter College of the City University of New York 1 , 695 Park Avenue, New York, New York 10065, USA; Department of Mathematics and Statistics, Hunter College of the City University of New York 2 , 695 Park Avenue, New York, New York 10065, USA

N

Norah M. Hoffmann

Department of Physics, Rutgers University 3 , Newark, New Jersey 07102, USA

L

Lionel Lacombe

Department of Physics, Rutgers University 3 , Newark, New Jersey 07102, USA

N

Neepa T. Maitra

Department of Physics, Rutgers University 3 , Newark, New Jersey 07102, USA

Funding

National Institutes of Health Award: 5R25GM060665-20

National Science Foundation Award: CHE-1940333

U.S. Department of Energy Award: DE-SC0020044

Cite This Article

Phillip Martinez, Bart Rosenzweig, Norah M. Hoffmann, et al. (2021). Case studies of the time-dependent potential energy surface for dynamics in cavities. The Journal of Chemical Physics, 154(1). https://doi.org/10.1063/5.0033386

Case studies of the time-dependent potential energy surface for dynamics in cavities

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