Picocavity-Controlled Subnanometer-Resolved Single-Molecule Fluorescence Imaging and Mollow Triplets

ABSTRACT: In this article, we address subnanometer resolved fluorescence imaging of single molecule inside a plasmonic picocavity by proposing a semiclassical theory via combining the macroscopic quantum electrodynamics theory and the open quantum system theory. To gain insights into the experimental 020-0677-y], we have further equipped this theory with the classical electromagnetic simulation of the picocavity, formed by atomistic cluster-decorated silver STM tip and a silver substrate, and the time-dependent density functional theory calculation of zinc phthalocyanine molecule. Our simulations not only reproduce the fluorescence spectrum and imaging as measured in the experiment, confirming the influence of extreme field confinement afforded by the picocavity, but also predict Rabi oscillation dynamics and Mollow triplets spectrum for moderate laser excitation. Thus, our study highlights the possibility of coherently manipulating the molecular state and exploring quantum optical phenomena with the plasmonic picocavity.

Automated summary

In this article, a semiclassical theory is proposed to study subnanometer resolved fluorescence imaging of single molecules inside a plasmonic picocavity. The theory combines macroscopic quantum electrodynamics and open quantum system theories. Classical electromagnetic simulation and time-dependent density functional theory calculations are used to simulate the formation of the picocavity and predict Rabi oscillation dynamics and Mollow triplets spectrum. The study highlights the potential of coherently manipulating molecular states and exploring quantum optical phenomena using plasmonic picocavities.