Using surface plasmonics to turn on fullerene's dark excitons

Using our recently proposed Bethe-Salpeter $G_0W_0$ formulation, we explore the optical absorption spectra of fullerene (C$_{60}$) near coinage metal surfaces (Cu, Ag, and Au). We pay special attention to how the surface plasmon $ω_S$ influences the optical activity of fullerene. We find the lower energy fullerene excitons at 3.77 and 4.8 eV only weakly interact with the surface plasmon. However, we find the surface plasmon strongly interacts with the most intense fullerene $π$ exciton, i.e.\ the dipolar mode at $\hbarω_+\approx$ 6.5 eV, and the quadrupolar mode at $\hbarω_-\approx$ 6.8 eV. When fullerene is close to a copper surface ($z_0\approx$ 5.3 Å) the dipolar mode $ω_+$ and "localized" surface plasmons in the molecule/surface interface hybridize to form two coupled modes which both absorb light. As a result, the molecule gains an additional optically active mode. Moreover, in resonance, when $ω_S\approxω_\pm$, the strong interaction with the surface plasmon destroys the $ω_-$ quadrupolar character and it becomes an optically active mode. In this case the molecule gains two additional very intense optically active modes. Further, we find this resonance condition, $ω_S \approx ω_\pm$, is satisfied by silver and gold metal surfaces.

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