Coupling electronic properties of molecules and materials to cavity optical modes: a road towards optical and chemical complexity

Overview & Synopsis

We investigate from the point of view of theory spectral and transport properties of open systems in interaction with electronic baths and photonic electromagnetic environments. We focus on three recent research fields for which this investigation is relevant and deal with the following questions of i) understanding how electronic transport properties (current and current-current fluctuations) of STM plasmonic nanojunctions correlate to their light-emission properties (luminescence spectra, g^2-measurements), ii) grasping how collective effects related to the intertwined dynamics between molecular aggregates and Fabry-Pérot cavity modes might be responsible for a modification of the embedded material chemical reactivity or chiroptical properties, and iii) how to model and characterize the stochastic dynamics of chemical reaction networks in concentrated molecular aggregates for ultrafast pump-probe experiments. In all those research directions our objective is to propose and develop some theoretical tools and methods that enable both analytical and numerical calculation of transport properties, spectroscopic signatures and characterization of physico-chemical properties of molecular ensembles going from the single-molecule limit to the mesoscopic aggregate in presence of interactions with a dynamical electromagnetic bath. We aim at initiating a discussion on how to incorporate in the modeling the necessary level of electronic, electromagnetic or chemical complexity found in the related experiments. This HDR thesis is an attempt to describe some interesting physical mechanisms I had the luck to find or think about during this research journey and to enlighten open questions in systems where the chemical and optical complexity is a relevant or key issue.