Fig. 4: Comparison of decay pathways.
From: Fluorescence from a single-molecule probe directly attached to a plasmonic STM tip
Calculated charge transfer rates γch for (a) the molecule lying flat and (b) standing upright on a semi-infinite jellium interface as a function of the distance a of the molecule from the jellium edge. The rates were calculated using the real-time wavepacket propagation method (WPP, squares) for orbitals shown in (c). The color of the frames in (c) corresponds to the color coding in (a, b). The dashed line in (a, b) corresponds to the maximum plasmon-induced decay rate γpl shown in (e) for the respective configurations. c Molecular orbitals LUMO, LUMO+1, and LUMO+2 calculated using the WPP approach for an isolated molecule (see Supplementary Eq. 3). The orbitals are evaluated 1a0 (a0 being the Bohr radius) above the plane of the molecule. d Transition charge density of the \({{{\rm{D}}}}_{1}^{-}\,\to \,{{{\rm{D}}}}_{0}^{-}\) transition calculated by TDDFT using Gaussian 16 rev. C.0150. e Plasmon-induced exciton decay rate as a function of the plasmonic resonance energy tuned by varying the length of the model plasmonic cavity (see Supplementary Fig. 5 for details of the geometry) calculated for the molecule in the upright configuration (blue) and the flat configuration (orange). The molecule is positioned in the middle of the tip-substrate gap which is 2.1 nm for the upright configuration and 1.1 nm for the flat one. Source data are provided as a Source Data file.
