Strong plasmon-molecule coupling at the nanoscale revealed by first-principles modeling

摘要: Strong light-matter interactions in both the single-emitter and collective strong coupling regimes attract significant attention due to emerging quantum nonlinear optics applications, as well opportunities for modifying material-related properties. Further exploration of these phenomena requires an appropriate theoretical methodology, which is demanding since polaritons are at intersection between optics, solid state physics chemistry. Fortunately, however, nanoscale can be realized small plasmon-molecule systems, principle allows treating them using ab initio methods, although this has not been demonstrated date. Here, we show that time-dependent density-functional theory (TDDFT) calculations access hybrids predict vacuum Rabi splitting a system comprising few-hundred-atom aluminum nanoparticle interacting with one or several benzene molecules. We cavity electrodynamics approach holds down resonators on order few cubic nanometers, yielding single-molecule strength exceeding 200 meV massive field value 4.5 V/nm. In broader perspective, our enables parameter-free in-depth studies polaritonic including ground state, chemical thermodynamic modifications molecules strong-coupling regime, may find important use applications such enhanced catalysis.