Time-frequency methods for coherent spectroscopy

Time-frequency decomposition techniques, borrowed from the signal-processing field, have been adapted and applied to the analysis of 2D oscillating signals. While the Fourier-analysis techniques available so far are able to interpret the information content of the oscillating signal only in terms of its frequency components, the time-frequency transforms (TFT) proposed in this work can instead provide simultaneously frequency and time resolution, unveiling the dynamics of the relevant beating components, and supplying a valuable help in their interpretation. In order to fully exploit the potentiality of this method, several TFTs have been tested in the analysis of sample 2D data. Possible artifacts and sources of misinterpretation have been identified and discussed

Correlated Fluctuations and Intraband Dynamics of J-Aggregates Revealed by Combination of 2DES Schemes

The intraband exciton dynamics of molecular aggregates is a crucial initial step to determine the possibly coherent nature of energy transfer and its implications for the ensuing interband relaxation pathways in strongly coupled excitonic systems. In this work, we fully characterize the intraband dynamics in linear J-aggregates of porphyrins, good model systems for multichromophoric assemblies in biological antenna complexes. Using different 2D electronic spectroscopy schemes together with Raman spectroscopy and theoretical modeling, we provide a full characterization of the inner structure of the main one-exciton band of the porphyrin aggregates. We find that the redistribution of population within the band occurs with a characteristic time of 280 fs and dominates the modulation of an electronic coherence. While we do not find that the coupling to vibrations significantly affects the dynamics of excitonic coherence, our results suggest that exciton fluctuations are nevertheless highly correlated

Global analysis of coherence and population dynamics in 2D electronic spectroscopy

2D electronic spectroscopy is a widely exploited tool to study excited state dynamics. A high density of information is enclosed in 2D spectra. A crucial challenge is to objectively disentangle all the features of the third order optical signal. We propose a global analysis method based on the variable projection algorithm, which is able to reproduce simultaneously coherence and population dynamics of rephasing and non-rephasing contributions. Test measures at room temperature on a standard dye are used to validate the procedure and to discuss the advantages of the proposed methodology with respect to the currently employed analysis procedures

Isolating the chiral contribution in optical two-dimensional chiral spectroscopy using linearly polarized light

The full development of mono- or multi-dimensional time-resolved spectroscopy techniques incorporating optical activity signals has been strongly hampered by the challenge of identifying the small chiral signals over the large achiral background. Here we propose a new methodology to isolate chiral signals removing the achiral background from two commonly used configurations for performing two dimensional optical spectroscopy, known as BOXCARS and GRadient Assisted Photon Echo Spectroscopy (GRAPES). It is found that in both cases an achiral signal from an isotropic system can be completely eliminated by small manipulations of the relative angles between the linear polarizations of the four input laser pulses. Starting from the formulation of a perturbative expansion of the signal in the angle between the beams and the propagation axis, we derive analytic expressions that can be used to estimate how to change the polarization angles of the four pulses to minimize achiral contributions in the studied configurations. The generalization to any other possible experimental configurations has also been discussed. %We derive analytic expressions to changes required to the polarizations in terms of a perturbative expansion in the angle between the beams and the colinear axis. We also numerically estimate higher order coefficients which cover arbitrarily large angles and thus any experimental configuration.Comment: 7 figure

Spectroscopy data for the time and frequency characterization of vibrational coherences in bacteriochlorophyll a

Bacteriochlorophyll is the primary pigment in the light-harvesting pigment-protein complexes (PPCs) of the bacterial photosynthetic apparatus. 2D electronic spectroscopy (2DES) represents one of the most exploited and powerful techniques to characterize the ultrafast relaxation dynamics in PPCs, in particular, to assess the presence of coherent mechanisms during energy transport.The data reported in this work and the associated research article, “Characterization of the coherent dynamics of bacteriochlorophyll a in solution” [Meneghin et al., 2019] are an important contribution to the literature on coherent dynamics of light-harvesting complexes and can be useful in the interpretation of coherent motion in more complex systems with bacteriochlorophyll a (BChla) as a basic unit. The analysis of the provided data allows the identification of vibrational coherences associated with several Franck-Condon active modes and the characterization of their frequencies and dephasing times.Here we report additional data analysis and additional measures that complement the associated research article [Meneghin et al., 2019] and support its main conclusions. In particular, we compare vibrational coherences extracted from 2DES response with Raman modes detected for BChla powders at cryogenic temperature in resonant and non-resonant conditions. Finally, we show the time-resolved fluorescence decay of the chromophore to support the interpretation of non-coherent dynamics discussed in Ref. [Meneghin et al., 2019]

Identification of Design Principles for the Preparation of Colloidal Plexcitonic Materials

: 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

Deciphering hot- and multi-exciton dynamics in core-shell QDs by 2D electronic spectroscopies

Although the harnessing of multiple and hot excitons is a prerequisite for many of the groundbreaking applications of semiconductor quantum dots (QDs), the characterization of their dynamics through conventional spectroscopic techniques is cumbersome. Here, we show how a careful analysis of 2DES maps acquired in different configurations (BOXCARS and pump–probe geometry) allows the tracking and visualization of intraband Auger relaxation mechanisms, driving the hot carrier cooling, and interband bi- and tri-exciton recombination dynamics. The results obtained on archetypal core– shell CdSe/ZnS QDs suggest that, given the global analysis of the resulting datasets, 2D electronic spectroscopy techniques can successfully and efficiently dispel the intertwined dynamics of fast and ultrafast recombination processes in nanomaterials. Hence, we propose this analysis scheme to be used in future research on novel quantum confined systems