The interactions of the excited states of a single chromophore with static and dynamic electric fields spatially varying at the atomic scale are investigated in a joint experimental and theoretical effort. In this configuration, the spatial extension of the fields confined at the apex of a scanning tunneling microscope tip is smaller than that of the molecular exciton, a property used to generate fluorescence maps of the chromophore with intramolecular resolution. Theoretical simulations of the electrostatic and electrodynamic interactions occurring at the picocavity junction formed by the chromophore, the tip, and the substrate reveal the key role played by subtle variations of Purcell, Lamb, and Stark effects. They also demonstrate that hyper-resolved fluorescence maps of the line shift and linewidth of the excitonic emission can be understood as images of the static charge redistribution upon electronic excitation of the molecule and as the distribution of the dynamical charge oscillation associated with the molecular exciton, respectively.

中文翻译：

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用超分辨荧光显微镜在发色团-皮腔连接处绘制 Lamb、Stark 和 Purcell 效应

在联合实验和理论工作中研究了单个发色团的激发态与在原子尺度上空间变化的静态和动态电场的相互作用。在这种配置中，限制在扫描隧道显微镜尖端的场的空间扩展小于分子激子的空间扩展，这是一种用于生成具有分子内分辨率的发色团荧光图的特性。对发色团、尖端和基板形成的微腔结处发生的静电和电动相互作用的理论模拟揭示了 Purcell、Lamb 和 Stark 效应的细微变化所起的关键作用。