arXiv subjects

Francesca Fassioli

Publications and source records attributed to Francesca Fassioli.

10 recordsLinked to original sources

arXiv2025

Tracking the photoinduced dynamics of a dark excitonic state in single-layer WS$_2$ via resonant Autler-Townes splitting

Excitons in a monolayer transition metal dichalcogenide (1L-TMD) are highly bound states characterized by a Rydberg-like spectrum of discrete energy levels. Among these, states with odd-parity are known as dark excitons due to selection rules, which make their stationary and transient characterization challenging using linear optical techniques. Here, we demonstrate that the dynamics of a 2p dark excitonic state in 1L-WS$_2$ can be directly retrieved by measuring the Autler-Townes splitting of bright states in a three-pulse experiment. The splitting of the bright 1s excitonic state, observed by detuning a mid-infrared control field across the 1s-2p transition, provides an accurate characterization of the 2p state. Following carrier photoinjection, we observe a qualitatively different dynamics of the 1s and 2p levels, which is indicative of symmetry-dependent screening and exciton-exciton interactions. These findings provide new insights into many-body effects in TMDs, offering potential avenues for advancing the next generation optoelectronics.

cond-mat.mes-hall↗

arXiv2024

Molecular Entanglement Witness by Absorption Spectroscopy in Cavity QED

Producing and maintaining molecular entanglement at room temperature and detecting multipartite entanglement features of macroscopic molecular systems remain key challenges for understanding inter-molecular quantum effects in chemistry. Here, we study the quantum Fisher information, a central concept in quantum metrology, as a multipartite entanglement witness. We generalize the entanglement witness functional related to quantum Fisher information regarding non-identical local response operators. We show that it is a good inter-molecular entanglement witness for ultrastrong light-matter coupling in cavity quantum electrodynamics, including near the superradiant phase transition. We further connect quantum Fisher information to the dipole correlator, which suggests that this entanglement could be detected by absorption spectroscopy. Our work proposes a general protocol to detect inter-molecular entanglement in chemical systems at room temperature.

quant-ph↗

arXiv2024

Controlling radiative heat flow through cavity electrodynamics

Cavity electrodynamics is emerging as a promising tool to control chemical processes and quantum material properties. In this work we develop a formalism to describe the cavity mediated energy exchange between a material and its electromagnetic environment. We show that coplanar cavities can significantly affect the heat load on the sample if the cavity resonance lies within the frequency region where free-space radiative heat dominates, typically the mid-IR at ambient temperature, while spectral filtering is necessary for having an effect with lower frequency cavities.

physics.optics↗

arXiv2023

Cavity-mediated thermal control of metal-to-insulator transition in 1T-TaS$_{2}$

Placing quantum materials into optical cavities provides a unique platform for controlling quantum cooperative properties of matter, via both weak and strong light-matter coupling. Here we report the experimental evidence of reversible cavity control of a metal-to-insulator phase transition in a correlated solid-state material. We embed the charge density wave material 1T-TaS$_{2}$ into cryogenic tunable terahertz cavities and show that a switch between conductive and insulating behaviors, associated with a large change in the sample temperature, is obtained by mechanically tuning the distance between the cavity mirrors and their alignment. The large thermal modification observed is indicative of a Purcell-like scenario in which the spectral profile of the cavity modifies the energy exchange between the material and the external electromagnetic field. Our findings provide opportunities for controlling the thermodynamics and macroscopic transport properties of quantum materials by engineering their electromagnetic environment.

cond-mat.mtrl-sci↗

arXiv2023

Manipulation of Charge Delocalization in a Bulk Heterojunction Material Using a Mid-Infrared Push Pulse

In organic bulk heterojunction materials, charge delocalization has been proposed to play a vital role in the generation of free carriers by reducing the Coulomb attraction via an interfacial charge transfer exciton (CTX). Pump-push-probe (PPP) experiments produced evidence that the excess energy given by a push pulse enhances delocalization, thereby increasing photocurrent. However, previous studies have employed near-IR push pulses in the range 0.4-0.6 eV which is larger than the binding energy of a typical CTX. This raises the doubt that the push pulse may directly promote dissociation without involving delocalized states. Here, we perform PPP experiments with mid-IR push pulses at energies that are well below the binding energy of a CTX state (0.12-0.25 eV). We identify three types of CTX: delocalized, localized, and trapped. The excitation resides over multiple polymer chains in delocalized CTXs, while is restricted to a single chain (albeit maintaining a degree of intrachain delocalization) in localized CTXs. Trapped CTXs are instead completely localized. The pump pulse generates a hot delocalized CTX, which relaxes to a localized CTX, and eventually to trapped states. We find that photo-exciting localized CTXs with push pulses resonant to the mid-IR charge transfer absorption can promote delocalization and contribute to the formation of long-lived charge separated states. On the other hand, we found that trapped CTX are non-responsive to the push pulses. We hypothesize that delocalized states identified in prior studies are only accessible in systems where there is significant interchain electronic coupling or regioregularity that supports either interchain or intrachain polaron delocalization. This emphasizes the importance of engineering the micromorphology and energetics of the donor-acceptor interface to exploit a full potential of a material for photovoltaic applications.

physics.chem-ph↗

arXiv2023

Femtosecond Photophysics of Molecular Polaritons

Molecular polaritons are hybrid states of photonic and molecular character that form when molecules strongly interact with light. Strong coupling tunes energy levels and importantly, can modify molecular properties (e.g. photoreaction rates) opening an avenue for novel polariton chemistry. In this perspective, we focus on the collective aspects of strongly coupled molecular systems and how this pertains to the dynamical response of such systems, which though of key importance for attaining modified function under polariton formation, is still not well understood. We discuss how the ultrafast time and spectral resolution make pump-probe spectroscopy an ideal tool to reveal the energy transfer pathways from polariton states to other molecular states of functional interest. Finally, we illustrate how analyzing the free (rather than electronic) energy structure in molecular polariton systems may provide new clues into how energy flows and thus how strong coupling may be exploited.

physics.chem-ph↗

arXiv2021

Toward Witnessing Molecular Exciton Entanglement from Spectroscopy

Entanglement is a defining feature of quantum mechanics that can be a resource in engineered and natural systems, but measuring entanglement in experiment remains elusive especially for large chemical systems. Most practical approaches require determining and measuring a suitable entanglement witness which provides some level of information about the entanglement structure of the probed state. A fundamental quantity of quantum metrology is the quantum Fisher information (QFI) which is a rigorous witness of multipartite entanglement that can be evaluated from linear response functions for certain states. In this work, we explore measuring the QFI of molecular exciton states of the first-excitation subspace from spectroscopy. In particular, we utilize the fact that the linear response of a pure state subject to a weak electric field over all possible driving frequencies encodes the variance of the collective dipole moment in the probed state, which is a valid measure for QFI. The systems that are investigated include the molecular dimer, $N$-site linear aggregate with nearest-neighbor coupling, and $N$-site circular aggregate, all modeled as a collection of interacting qubits. Our theoretical analysis shows that the variance of the collective dipole moment in the brightest dipole-allowed eigenstate is the maximum QFI. The optical response of a thermally equilibrated state in the first-excitation subspace is also a valid QFI. Theoretical predictions of the measured QFI for realistic linear dye aggregates as a function of temperature and energetic disorder due to static variations of the host matrix show that 2- to 3-partite entanglement is realizable. This work lays some groundwork and inspires measurement of multipartite entanglement of molecular excitons with ultrafast pump-probe experiments.

quant-ph↗

arXiv2013

Dynamical transitions in Markovian exciton transport

The large deviation theory has recently been applied to open quantum systems to uncover dynamical crossovers in the space of quantum trajectories associated to Markovian evolutions. Such dynamical crossovers are characterized by qualitative changes in the fluctuations of rare quantum jump trajectories, and have been observed in the statistics of coherently driven quantum systems. In this article we investigate the counting statistics of rare quantum trajectories of an undriven system undergoing a pure relaxation process, namely, Markovian exciton transport. We find that dynamical crossovers occur in systems with a minimum of three interacting molecules, and are strongly activated by exciton delocalization and interference. Our results illustrate how quantum features of the underlying system Hamiltonian can influence the statistical properties of energy transfer processes in a non-trivial manner.

quant-ph↗

arXiv2010

Quantum State Tuning of Energy Transfer in a Correlated Environment

We investigate multichromophoric energy transfer allowing for bath-induced fluctuations at different sites to be correlated. As a prototype system we consider a light-harvesting antenna surrounding a reaction center. We show that the interplay between quantum coherence and correlated fluctuations can generate a room temperature transfer process featuring a marked dependence on the degree of symmetry and delocalization of the initial exciton state. Our work illustrates how these quantum features could support fine tuning of energy transfer efficiencies in closely-packed natural and artificial light-harvesting complexes

quant-ph↗

arXiv2010

Distribution of entanglement in light-harvesting complexes and their quantum efficiency

Recent evidence of electronic coherence during energy transfer in photosynthetic antenna complexes has reinvigorated the discussion of whether coherence and/or entanglement has any practical functionality for these molecular systems. Here we investigate quantitative relationships between the quantum yield of a light-harvesting complex and the distribution of entanglement among its components. Our study focusses on the entanglement yield or average entanglement surviving a time scale comparable to the average excitation trapping time. As a prototype system we consider the Fenna-Matthews-Olson (FMO) protein of green sulphur bacteria and show that there is an inverse relationship between the quantum efficiency and the average entanglement between distant donor sites. Our results suggest that longlasting electronic coherence among distant donors might help modulation of the lightharvesting function.

quant-ph↗