Managing temperature in open quantum systems strongly coupled with structured environments.

In non-perturbative non-Markovian open quantum systems, reaching either low temperatures with the hierarchical equations of motion (HEOM) or high temperatures with the Thermalized Time Evolving Density Operator with Orthogonal Polynomials Algorithm (T-TEDOPA) formalism in Hilbert space remains challenging. We compare different ways of modeling the environment. Sampling the Fourier transform of the bath correlation function, also called temperature dependent spectral density, proves to be very effective. T-TEDOPA [Tamascelli et al., Phys. Rev. Lett. 123, 090402 (2019)] uses a linear chain of oscillators with positive and negative frequencies, while HEOM is based on the complex poles of an optimized rational decomposition of the temperature dependent spectral density [Xu et al., Phys. Rev. Lett. 129, 230601 (2022)]. Resorting to the poles of the temperature independent spectral density and of the Bose function separately is an alternative when the problem due to the huge number of Bose poles at low temperatures is circumvented. Two examples illustrate the effectiveness of the HEOM and T-TEDOPA approaches: a benchmark pure dephasing case and a two-bath model simulating the dynamics of excited electronic states coupled through a conical intersection. We show the efficiency of T-TEDOPA to simulate dynamics at a finite temperature by using either continuous spectral densities or only all the intramolecular oscillators of a linear vibronic model calibrated from ab initio data of a phenylene ethynylene dimer.

Thermoresponsive Fluorescence Switches Based on Au@pNIPAM Nanoparticles.

Despite numerous studies emphasizing the plasmonic impact on fluorescence, the design of a dynamic system allowing on-demand fluorescence switching in a single nanostructure remains challenging. The reversibility of fluorescence switching and the versatility of the approach, in particular its compatibility with a wide range of nanoparticles and fluorophores, are among the main experimental difficulties. In this work, we achieve reversible fluorescence switching by coupling metal nanoparticles with fluorophores through stimuli-responsive organic linkers. As a proof of concept, we link gold nanoparticles with fluorescein through thermoresponsive poly(N-isopropylacrylamide) at a tunable grafting density and characterize their size and optical response by dynamic light scattering, absorption, and fluorescence spectroscopies. We show that the fluorescence emission of these hybrid nanostructures can be switched on-demand using the thermoresponsive properties of poly(N-isopropylacrylamide). The described system presents a general strategy for the design of nanointerfaces, exhibiting reversible fluorescence switching via external control of metal nanoparticle/fluorophore distance.