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

Juan B. Pérez-Sánchez, Arghadip Koner, Nathaniel P. Stern, Joel Yuen-Zhou*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

3 Scopus citations


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.

Original languageEnglish (US)
Article numbere2219223120
JournalProceedings of the National Academy of Sciences of the United States of America
Issue number15
StatePublished - Apr 11 2023


  • collective strong-coupling regime
  • permutational symmetries
  • polariton chemistry
  • quantum dynamics

ASJC Scopus subject areas

  • General


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