Multidimensional Quantum Dynamical Simulation of Infrared Spectra under Polaritonic Vibrational Strong Coupling.

Recent experimental and theoretical studies demonstrate that the chemical reactivity of molecules can be modified inside an optical cavity. Here, we provide a theoretical framework for conducting multidimensional quantum simulations of the infrared (IR) spectra for molecules interacting with cavity modes. A single water molecule under polaritonic vibrational strong coupling serves as an illustrative example. Combined with accurate potential energy and dipole moment surfaces, our cavity vibrational self-consistent field/virtual state configuration interaction (cav-VSCF/VCI) approach can predict the IR spectra when the molecule is inside or outside the cavity. The spectral signatures of Rabi splittings and shifts of certain bands are found to be strongly dependent on the frequency and polarization direction of the cavity modes. Analyses of the simulated spectra show that polaritonic vibrational strong coupling can induce unconventional couplings among the molecule's vibrational modes, suggesting that intramolecular vibrational energy transfer can be significantly accelerated by the cavity.