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Title: Simulating molecular polaritons in the collective regime using few-molecule models

Abstract

The study of molecular polaritons beyond simple quantum emitter ensemble models (e.g., Tavis–Cummings) is challenging due to the large dimensionality of these systems and the complex interplay of molecular electronic and nuclear degrees of freedom. This complexity constrains existing models to either coarse-grain the rich physics and chemistry of the molecular degrees of freedom or artificially limit the description to a small number of molecules. In this work, we exploit permutational symmetries to drastically reduce the computational cost of ab initio quantum dynamics simulations for large N . Furthermore, we discover an emergent hierarchy of timescales present in these systems, that justifies the use of an effective single molecule to approximately capture the dynamics of the entire ensemble, an approximation that becomes exact as N → ∞. We also systematically derive finite N corrections to the dynamics and show that addition of k extra effective molecules is enough to account for phenomena whose rates scale as 𝒪( N − k ). Based on this result, we discuss how to seamlessly modify existing single-molecule strong coupling models to describe the dynamics of the corresponding ensemble. We call this approach collective dynamics using truncated equations (CUT-E), benchmark it against well-knownmore » results of polariton relaxation rates, and apply it to describe a universal cavity-assisted energy funneling mechanism between different molecular species. Beyond being a computationally efficient tool, this formalism provides an intuitive picture for understanding the role of bright and dark states in chemical reactivity, necessary to generate robust strategies for polariton chemistry.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, CA 92093
  2. Department of Physics and Astronomy, Northwestern University, Evanston, IL 60208
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1968647
Grant/Contract Number:  
SC0021314
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 120 Journal Issue: 15; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English

Citation Formats

Pérez-Sánchez, Juan B., Koner, Arghadip, Stern, Nathaniel P., and Yuen-Zhou, Joel. Simulating molecular polaritons in the collective regime using few-molecule models. United States: N. p., 2023. Web. doi:10.1073/pnas.2219223120.
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Pérez-Sánchez, Juan B., Koner, Arghadip, Stern, Nathaniel P., & Yuen-Zhou, Joel. Simulating molecular polaritons in the collective regime using few-molecule models. United States. https://doi.org/10.1073/pnas.2219223120
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Pérez-Sánchez, Juan B., Koner, Arghadip, Stern, Nathaniel P., and Yuen-Zhou, Joel. Thu . "Simulating molecular polaritons in the collective regime using few-molecule models". United States. https://doi.org/10.1073/pnas.2219223120.
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@article{osti_1968647,
title = {Simulating molecular polaritons in the collective regime using few-molecule models},
author = {Pérez-Sánchez, Juan B. and Koner, Arghadip and Stern, Nathaniel P. and Yuen-Zhou, Joel},
abstractNote = {The study of molecular polaritons beyond simple quantum emitter ensemble models (e.g., Tavis–Cummings) is challenging due to the large dimensionality of these systems and the complex interplay of molecular electronic and nuclear degrees of freedom. This complexity constrains existing models to either coarse-grain the rich physics and chemistry of the molecular degrees of freedom or artificially limit the description to a small number of molecules. In this work, we exploit permutational symmetries to drastically reduce the computational cost of ab initio quantum dynamics simulations for large N . Furthermore, we discover an emergent hierarchy of timescales present in these systems, that justifies the use of an effective single molecule to approximately capture the dynamics of the entire ensemble, an approximation that becomes exact as N → ∞. We also systematically derive finite N corrections to the dynamics and show that addition of k extra effective molecules is enough to account for phenomena whose rates scale as 𝒪( N − k ). Based on this result, we discuss how to seamlessly modify existing single-molecule strong coupling models to describe the dynamics of the corresponding ensemble. We call this approach collective dynamics using truncated equations (CUT-E), benchmark it against well-known results of polariton relaxation rates, and apply it to describe a universal cavity-assisted energy funneling mechanism between different molecular species. Beyond being a computationally efficient tool, this formalism provides an intuitive picture for understanding the role of bright and dark states in chemical reactivity, necessary to generate robust strategies for polariton chemistry.},
doi = {10.1073/pnas.2219223120},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 15,
volume = 120,
place = {United States},
year = {Thu Apr 06 00:00:00 EDT 2023},
month = {Thu Apr 06 00:00:00 EDT 2023}
}
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https://doi.org/10.1073/pnas.2219223120
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