Speaker
Description
Discrepancy between atomistic molecular dynamics and experiment can arise, among other things, from the difference in the number of molecules that are considered, making the direct comparison between simulation and experiment often ambiguous. Especially for investigating phenomena that directly depend on the number of molecules, such as strong coupling between light and matter, a meaningful direct comparison would be highly desirable to gain understanding from both methods. Plasmonic nanocavities have been experimentally reported to provide an environment supporting few or even single-molecule strong coupling [1,2], making them ideal templates to build atomistic simulation models [3] with as many (or as few) molecules as in experiment and thus enable more direct comparison. The atomistic resolution of the simulations provides valuable insights into conditions governing strong coupling in terms of the system’s geometry, conformation and dynamics, improving understanding and promoting design of new systems. As a proof of concept of such simulation platform, we present an atomistic model of the full plasmonic nanocavity system in reference [1] consisting of the gold nanoparticle on top of the gold surface (nanoparticle-on-mirror geometry) with the emitter molecule(s) (methylene blue) encapsulated by scaffold molecules (cucurbit-[7]-uril) in the gap region.
[1] Chikkaraddy R, de Nijs B, Benz F, et al. Single-molecule strong coupling at room temperature in plasmonic nanocavities. Nature. 2016;535(7610):127-130. doi:10.1038/nature17974.
[2] Heintz J, Markešević N, Gayet E, et al. Few-Molecule Strong Coupling with Dimers of Plasmonic Nanoparticles Assembled on DNA. ACS Nano. 2021;15(9):14732-14743. doi: 10.1021/acsnano.1c04552.
[3] Luk HL, Feist J, Toppari JJ, Groenhof G. Multiscale Molecular Dynamics Simulations of Polaritonic Chemistry. J Chem Theory Comput. 2017; 12;13(9):4324-4335. doi: 10.1021/acs.jctc.7b00388.
