Fully Quantum Simulation of Polaritonic Vibrational Spectra of Large Cavity-Molecule System

The formation of molecular vibrational polaritons, arising from the interplay between molecular vibrations and infrared cavity modes, is a quantum phenomenon necessitating accurate quantum dynamical simulations. Here, we introduce the cavity vibrational self-consistent field/virtual state configuration interaction method, enabling quantum simulation of the vibrational spectra of many-molecule systems within the optical cavity. Focusing on the representative (H₂O)₂₁ system, we showcase this parameter-free quantum approach’s ability to capture both linear and nonlinear vibrational spectral features. Our findings highlight the growing prominence of molecular couplings among OH stretches and bending excited bands with increased light-matter interaction, revealing distinctive nonlinear spectral features induced by vibrational strong coupling.