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  • Open Access

Nonlinear spectroscopy of cavity polaritons

Anqi Li1, Upendra Harbola2, and Michael Galperin3,*

  • *Contact author: mgalperin@tauex.tau.ac.il
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Phys. Rev. Research 7, 033248 – Published 12 September, 2025

DOI: https://doi.org/10.1103/ccfc-1fg4

Abstract

Confinement of molecules within a cavity leads to a strong coupling between light and matter degrees of freedom, merging the two into a quasiparticle known as a polariton. Theoretical treatments of molecular polaritons generally utilize either exact diagonalization of the interacting molecule-cavity system Hamiltonian or perturbation theory to analyze intracavity light-matter interactions. The former is constrained in its capacity to account for the open nature of the molecular cavity system, while the treatment of strong interactions within perturbation theory represents a weakness of the latter. Here, we introduce a pseudoparticle nonequilibrium Green's function (PP-NEGF) formulation for molecular polariton spectroscopy. This formulation addresses the limitations of currently available approaches by accounting for all intrasystem interactions exactly and treating system-bath couplings within diagrammatic expansion and extends a recent NEGF-based formulation for nonlinear optical spectroscopy [J. Chem. Phys. 162, 074108 (2025)] to strongly interacting molecular systems. Theoretical derivations are demonstrated through numerical simulations, where we examine the impact of strong light-matter interaction on fluxes and multidimensional optical spectroscopy of cavity polaritons.

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Phys. Rev. Research 7, 033248– Published 12 September, 2025
  • Received 3 June 2025
  • Accepted 21 August 2025
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Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.

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