Toward collective chemistry by strong light-matter coupling

Abstract

Strong light-matter coupling provides a versatile and novel means to manipulate chemical processes. Here we develop a theoretical framework to investigate the spectroscopy and dynamics of a molecular ensemble embedded in an optical cavity under the collective strong coupling regime. This theory is constructed by a pseudoparticle representation of the molecular Hamiltonians, mapping the polaritonic Hamiltonian into a coupled fermion-boson model under particle number constraints. The mapped model is then analyzed using the non-equilibrium Green function theory with the important self-energy diagrams identified through power counting. Numerical demonstrations are shown for the driven Tavis-Cummings model, which shows an excellent agreement with exact results.