We investigate the spectral features of Action-2D Electronic Spectroscopy (A-2DES) using a molecular dimer model across different regimes of excitonic coupling. By explicitly including a second-excited state for each chromophore, we simulate A-2DES spectra ranging from the non-interacting limit to the strong-coupling case, focusing on the significance of cross peaks. While for weak excitonic coupling, cross peaks can be understood as the incoherent mixing of linear signals of the two chromophores, these features reflect excitonic delocalization as the coupling increases. We highlight that A-2DES offers enhanced sensitivity to coherent excited-state dynamics, particularly in the intermediate-coupling regime, where it provides higher contrast compared to its coherent-detected counterpart. Finally, we show the different influences of static disorder on the line shapes of diagonal and cross peaks. Notably, since cross peaks exhibit rephasing capability for increasing excitonic coupling, the contribution of incoherent mixing becomes less significant in inhomogeneous samples. These findings support the potential of A-2DES for investigating excitonic dynamics in small multi-chromophoric systems.

Including the effect of the molecular environment in the numerical modeling of time-resolved electronic spectroscopy remains an important challenge in computational spectroscopy. In this contribution, we present a general approach for the simulation of the optical response of multichromophore systems in a structured environment and its implementation as a quantum algorithm. A key step of the procedure is the pseudomode embedding of the system-environment problem resulting in a finite set of quantum states evolving according to a Markovian quantum master equation. This formulation is then solved by a collision model integrated into a quantum algorithm designed to simulate linear and nonlinear response functions. The workflow is validated by simulating spectra for the prototypical excitonic dimer interacting with fast (memoryless) and finite-memory environments. The results demonstrate, on the one hand, the potential of the pseudomode embedding for simulating the dynamical features of nonlinear spectroscopy, including lineshape, spectral diffusion, and relaxations along delay times. On the other hand, the explicit synthesis of quantum circuits provides a fully quantum simulation protocol of nonlinear spectroscopy harnessing the efficient quantum simulation of many-body dynamics promised by the future generation of fault-tolerant quantum computers.

Multidimensional optical spectroscopies are powerful techniques to investigate energy transfer pathways in natural and artificial systems. Because of the high information content of the spectra, numerical simulations of the optical response are of primary importance to assist the interpretation of spectral features. However, the increasing complexity of the investigated systems and their quantum dynamics call for the development of novel simulation strategies. In this work, we consider using digital quantum computers. By combining quantum dynamical simulation and nonlinear response theory, we present a quantum algorithm for computing the optical response of molecular systems. The quantum advantage stems from the efficient quantum simulation of the dynamics governed by the molecular Hamiltonian, and it is demonstrated by explicitly considering exciton-vibrational coupling. The protocol is tested on a near-term quantum device, providing the digital quantum simulation of the linear and nonlinear response of simple molecular models.

The unraveling of open quantum system dynamics in terms of stochastic quantum trajectories offers a picture of open system dynamics that consistently considers memory effects stemming from the finite correlation time of environment fluctuations. These fluctuations significantly influence the coherence and energy transport properties of excitonic systems. When their correlation time is comparable to the timescale of the Hamiltonian evolution, it leads to the departure of open system dynamics from the Markovian limit. In this work, we leverage the unraveling of exciton dynamics through stochastic Hamiltonian propagators to design quantum circuits that simulate exciton transport, capturing finite memory effects. In addition to enabling the synthesis of parametrizable quantum circuits, stochastic unitary propagators provide a transparent framework for investigating non-Markovian effects on exciton transport. Our analysis reveals a nuanced relationship between environment correlation time and transport efficiency, identifying a regime of "memory-assisted" quantum transport where time-correlated fluctuations allow the system to reach higher efficiency. However, this property is not universal and can only be realized in conjunction with specific features of the system Hamiltonian.

We present a nonlinear spectroelectrochemical technique to investigate photosynthetic protein complexes. The PEC2DES setup combines photoelectrochemical detection (PEC) that selectively probes the protein photogenerated charges output with two-dimensional electronic spectroscopy (2DES) excitation that spreads the nonlinear optical response of the system in an excitation-detection map. PEC allows us to distinguish the contribution of charge separation (CS) from other de-excitation pathways, whereas 2DES allows us to disentangle congested spectral bands and evaluate the exciton dynamics (decays and coherences) of the photosystem complex. We have developed in operando phase-modulated 2DES by measuring the photoelectrochemical reaction rate in a biohybrid electrode functionalized with a plant photosystem complex I-light harvesting complex I (PSI-LHCI) layer. Optimizing the photoelectrochemical current signal yields reliable linear spectra unequivocally associated with PSI-LHCI. The 2DES signal is validated by nonlinear features like the characteristic vibrational coherence at 750 cm-1. However, no energy transfer dynamics is observed within the 450 fs experimental window. These intriguing results are discussed in the context of incoherent mixing resulting in reduced nonlinear contrast for multichromophoric complexes, such as the 160 chlorophyll PSI. The presented PEC2DES method identifies generated charges unlike purely optical 2DES and opens the way to probe the CS channel in multichromophoric complexes.

Action-detection has expanded the scope and applicability of 2D electronic spectroscopy, while posing new challenges for the unambiguous interpretation of spectral features. In this context, identifying the origin of cross-peaks at early waiting times is not trivial, and incoherent mixing is often invoked as an unwanted contribution masking the nonlinear signal. In this work, we elaborate on the relation between the nonlinear response and the incoherent mixing contribution by analyzing the action signal in terms of one- and two-particle observables. Considering a weakly interacting molecular dimer, we show how cross-peaks at early waiting times, reflecting exciton–exciton annihilation dynamics, can be equivalently interpreted as arising from incoherent mixing. This equivalence, on the one hand, highlights the information content of spectral features related to incoherent mixing and, on the other hand, provides an efficient numerical scheme to simulate the action response of weakly interacting systems.

This study elucidates the information content that is extracted from action-2D electronic spectroscopy (A-2DES) when the output intensity is not proportional to the number of excitations generated. Such a scenario can be realized in both fluorescence and photocurrent detection because of direct interaction like exciton-exciton annihilation or indirect effects in the signal generation or detection. By means of an intuitive probabilistic model supported by nonlinear response theory, the study concludes that in molecular assemblies the ground-state bleaching contribution can dominate the nonlinear signal and partially or completely hide the stimulated emission. In this case, the spectral effect resembles incoherent mixing, even in the absence of exciton-exciton annihilation, implying reduced information about the excited-state dynamics with an increasing number of chromophores. This finding has important implications for the selection of samples for A-2DES as well as for its interpretation.

Colloidal plexcitonic materials (CPMs) are a class of nanosystems where molecular dyes are strongly coupled with colloidal plasmonic nanoparticles, acting as nanocavities that enhance the light field. As a result of this strong coupling, new hybrid states are formed, called plexcitons, belonging to the broader family of polaritons. With respect to other families of polaritonic materials, CPMs are cheap and easy to prepare through wet chemistry methodologies. Still, clear structure-to-properties relationships are not available, and precise rules to drive the materials' design to obtain the desired optical properties are still missing. To fill this gap, in this article, we prepared a dataset with all CPMs reported in the literature, rationalizing their design by focusing on their three main relevant components (the plasmonic nanoparticles, the molecular dyes, and the capping layers) and identifying the most used and efficient combinations. With the help of statistical analysis, we also found valuable correlations between structure, coupling regime, and optical properties. The results of this analysis are expected to be relevant for the rational design of new CPMs with controllable and predictable photophysical properties to be exploited in a vast range of technological fields.

Simulating charge and energy transfer in extended molecular networks requires an effective model to include the environment because it significantly affects the quantum dynamics. A prototypical effect known as environment-assisted quantum transport (ENAQT) consists in the enhancement of the transfer efficiency by the interaction with an environment. A simple description of this phenomenon is obtained by a quantum master equation describing a quantum walk over the molecular network in the presence of inter-site decoherence. We consider the problem of simulating the dynamics underlying ENAQT in a digital quantum computer. Two different quantum algorithms are introduced, the first one based on stochastic Hamiltonians and the second one based on a collision scheme. We test both algorithms by simulating ENAQT in a small molecular network on a quantum computer emulator and provide a comparative analysis of the two approaches. Both algorithms can be implemented in a memory efficient encoding with the number of required qubits scaling logarithmically with the size of the simulated system while the number of gates increases quadratically. We discuss the algorithmic quantum trajectories generated by the two simulation strategies showing that they realize distinct unravellings of the site-dephasing master equation. In our approach, the non-unitary dynamics of the open system is obtained through effective representations of the environment, paving the way to digital quantum simulations of quantum transport influenced by structured environments.

Action-2D electronic spectroscopy is emerging as a powerful technique to investigate exciton dynamics in molecular aggregates and nanostructures. While maintaining the power of highlighting coherent evolution between the laser pulses, action detection is based on measuring the incoherent signal proportional to the excited-state populations generated by an additional laser pulse. Numerical simulations of the action signal play a crucial role in aiding the interpretation of the spectral features, which may differ from those of the analog coherent technique in a non-trivial way. We present a numerical investigation of the action response of a model of quantum dot as a case study to unravel the exciton and biexciton contributions in the 2D-spectra of nanostructures. The simulation protocol is based on a non-perturbative treatment of the light-matter interaction by solving the Lindblad quantum master equation and the different contributions to the non-linear response are disentangled using a phase-modulation scheme. We analyze how the relative weights of the exciton and biexciton signals determine the lineshape of the spectrum, how they depend upon the physical nature of the detected signal, i.e., fluorescence or photocurrent, and on the relaxation dynamics during the detection-time. Compatibly with the experimental conditions, the choice of the detection-mode and the use of time-gating may eventually facilitate the evaluation of relevant parameters, such as the biexciton binding energy and the timescale of the biexciton relaxation.

The biological activity of sulfur and selenium, despite their similarity, shows some remarkable differences that have been recognized in many different scenarios.

The reactivity of diselenides and ditellurides of general formula (RX)2 (X = Se, Te; R = H, CH3, Ph) toward hydrogen peroxide was studied through a computational approach based on accurate Density Functional Theory (DFT) calculations. The aliphatic and aromatic dichalcogenides have been chosen in light of their activity in glutathione peroxidase (GPx)-like catalytic cycles and their promising features as efficient antioxidant compounds. The reaction products, the energetics and the mechanistic details of these oxidations are discussed. Analogous disulfides are included in our analysis for completeness. We find that the barrier for oxidation of dichalcogenides decreases from disulfides to diselenides to ditellurides. On the other hand, variation of the substituents at the chalcogen nucleus has relatively little effect on the reactivity.