Vibrational Dressing of Collective Molecular Polaritons: A Scalable Green's-Function Theory

Abstract

We develop a scalable Green's-function theory of vibrationally dressed molecular-polariton absorption in the Holstein--Tavis--Cummings model. Within the self-consistent Born approximation (SCBA), the ground-state linear response of $N$ identical molecules coupled to one cavity mode follows from a $2\times 2$ cavity--bright matrix, while scattering through the $N-1$ dark states remains in the molecular self-energy. The number of self-consistent equations is independent of $N$, allowing large ensembles to be treated without explicitly resolving the dark manifold. Benchmarks against hierarchical equations of motion show that the theory captures collective linewidth narrowing and an $N$-dependent minimum in the lower-polariton linewidth as its exciton fraction varies, beyond a Hopfield-weighted linewidth estimate. Comparisons with exact diagonalization for discrete local vibrations show weaker vibronic progressions and better overall SCBA agreement as $N$ increases at fixed single-molecule coupling. The resulting framework connects microscopic vibrational scattering to collective absorption spectra without introducing fitted polariton linewidths.

arXiv comment8 pages, 4 figures