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The fluorescence response of a chromophore in the proximity of a plasmonic nanostructure can be enhanced by several orders of magnitude, yielding the so-called surface-enhanced fluorescence (SEF). An in-depth understanding of SEF mechanisms benefits from fully atomistic theoretical models because SEF signals can be non-trivially affected by the atomistic profile of the nanostructure's surface. This work presents the first fully atomistic multiscale approach to SEF, capable of describing realistic structures. The method is based on coupling density functional theory (DFT) with state-of-the-art atomistic electromagnetic approaches, allowing for reliable physically-based modeling of molecule-nanostructure interactions. Computed results remarkably demonstrate the key role of the NP morphology and atomistic features in quenching/enhancing the fluorescence signal., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

In the present work, we apply recently developed real-time descriptors to study the time evolution of plasmonic features of pentagonal Ag clusters. The method is based on the propagation of the time-dependent Schrödinger equation within a singly excited TDDFT ansatz. We use transition contribution maps (TCMs) and induced density to characterize the optical longitudinal and transverse response of such clusters, when interacting with pulses resonant with the low-energy (around 2-3 eV, A1) size-dependent or the high-energy (around 4 eV, E1) size-independent peak. TCMs plots on the analyzed clusters, Ag25+ and Ag43+ show off-diagonal peaks consistent with a plasmonic response when a longitudinal pulse resonant at A1 frequency is applied, and dominant diagonal spots, typical of a molecular transition, when a transverse E1 pulse is employed. Induced densities confirm this behavior, with a dipole-like charge distribution in the first case. The optical features show a time delay with respect to the evolution of the external pulse, consistent with those found in the literature for real-time TDDFT calculations on metal clusters.