Mapping Lamb, Stark and Purcell effects at a chromophore-picocavity junction with hyper-resolved fluorescence microscopy

TL;DR

This study combines experimental fluorescence microscopy and theoretical modeling to map and understand the Lamb, Stark, and Purcell effects at a chromophore-picocavity junction with sub-molecular resolution.

Contribution

It introduces a method to generate hyper-resolved fluorescence maps of chromophores influenced by picometer-scale plasmonic cavities, revealing subtle quantum effects.

Findings

Fluorescence maps with intra-molecular resolution were successfully generated.

Theoretical simulations accurately reproduce experimental fluorescence patterns.

Key roles of Purcell, Lamb, and Stark effects at the junction were identified.

Abstract

The interactions between the excited states of a single chromophore with static and dynamic electric fields confined to a plasmonic cavity of picometer dimensions are investigated in a joint experimental and theoretical effort. In this configuration, the spatial extensions of the confined fields are smaller than the one of the molecular exciton, a property that is used to generate fluorescence maps of the chromophores with intra-molecular resolution. Theoretical simulations of the electrostatic and electrodynamic interactions occurring at the chromophore-picocavity junction are able to reproduce and interpret these hyper-resolved fluorescence maps, and reveal the key role played by subtle variations of Purcell, Lamb and Stark effects at the chromophore-picocavity junction.