Phase-modulated rapid-scanning fluorescence-detected two-dimensional electronic spectroscopy

Agathangelou, Damianos; Javed, Ariba; Sessa, Francesco; Solinas, Xavier; Ogilvie, Jennifer P.

doi:10.1063/5.0057649

Cited by 21 publications

(14 citation statements)

References 32 publications

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“…Both are beyond our current experimental resolution. This could be solved by deploying advanced sampling strategies 67 – 69 or implementing frequency-comb technology 53 in order to increase the resolution to the required regime, thus, opening a promising perspective for the study of solvation mechanisms in superfluid environments.…”

Section: Resultsmentioning

confidence: 99%

High-resolution two-dimensional electronic spectroscopy reveals the homogeneous line profile of chromophores solvated in nanoclusters

2022

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Doped clusters in the gas phase provide nanoconfined model systems for the study of system-bath interactions. To gain insight into interaction mechanisms between chromophores and their environment, the ensemble inhomogeneity has to be lifted and the homogeneous line profile must be accessed. However, such measurements are very challenging at the low particle densities and low signal levels in cluster beam experiments. Here, we dope cryogenic rare-gas clusters with phthalocyanine molecules and apply action-detected two-dimensional electronic spectroscopy to gain insight into the local molecule-cluster environment for solid and superfluid cluster species. The high-resolution homogeneous linewidth analysis provides a benchmark for the theoretical modelling of binding configurations and shows a promising route for high-resolution molecular two-dimensional spectroscopy.

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Section: Resultsmentioning

confidence: 99%

High-resolution two-dimensional electronic spectroscopy reveals the homogeneous line profile of chromophores solvated in nanoclusters

2022

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“…In experiments with population detection, the signals I bold-italick p d in the desired phase-matching directions k are frequently extracted by the phase-modulation procedure pioneered by Marcus and co-workers and recently extended by Ogilvie and co-workers . This procedure was mimicked in spectroscopic EOM simulations of population-detected signals. , However, the numerical implementation of phase modulation is inefficient, since long-time (∼10–100 ps) propagations of driven MEs or TDSEs are required.…”

Section: Population-detected Signalsmentioning

confidence: 99%

Equation-of-Motion Methods for the Calculation of Femtosecond Time-Resolved 4-Wave-Mixing and N-Wave-Mixing Signals

2022

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Femtosecond nonlinear spectroscopy is the main tool for the time-resolved detection of photophysical and photochemical processes. Since most systems of chemical interest are rather complex, theoretical support is indispensable for the extraction of the intrinsic system dynamics from the detected spectroscopic responses. There exist two alternative theoretical formalisms for the calculation of spectroscopic signals, the nonlinear response-function (NRF) approach and the spectroscopic equation-of-motion (EOM) approach. In the NRF formalism, the system–field interaction is assumed to be sufficiently weak and is treated in lowest-order perturbation theory for each laser pulse interacting with the sample. The conceptual alternative to the NRF method is the extraction of the spectroscopic signals from the solutions of quantum mechanical, semiclassical, or quasiclassical EOMs which govern the time evolution of the material system interacting with the radiation field of the laser pulses. The NRF formalism and its applications to a broad range of material systems and spectroscopic signals have been comprehensively reviewed in the literature. This article provides a detailed review of the suite of EOM methods, including applications to 4-wave-mixing and N-wave-mixing signals detected with weak or strong fields. Under certain circumstances, the spectroscopic EOM methods may be more efficient than the NRF method for the computation of various nonlinear spectroscopic signals.

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“…Construction of fMES dataset requires signal collection at each time delay along the delay axes (t 21 ,T , t 43 ). Even though noisy data points near zero delay affect the signal the most, typically delay scans for each T have been done 8 by sampling the optical coherence axes (corresponding to delays t 21 and t 43 ) as a uniform (t 21 ,t 43 ) grid, through either stepwise or continuous stage scanning 17 , or through a pulse shaper 9 . Fig.…”

Section: Data Collection Schemementioning

confidence: 99%

“…This manuscript explores the sensitivity limits of the AOPM-based dynamic phase cycling approach to fMES. One way to improve sensitivity is through reductions in data collection time, such as the recent demonstration 17 of rephasing and non-rephasing 2D spectra at a single waiting time T through rapid stage scan along the optical coherence axes. This demonstration is especially relevant in the context of spatially-resolved measurements when all other fMES approaches reported 8 so far have relied on two orders of magnitude higher repetition rates.…”

Section: Introductionmentioning

confidence: 99%

High-sensitivity Fluorescence-Detected Multidimensional Electronic Spectroscopy Through Continuous Pump-probe Delay Scan

Sahu¹,

Bhat²,

Patra³

et al. 2022

Preprint

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Background-free fluorescence detection in multidimensional electronic spectroscopy promises high sensitivity compared to conventional approaches. Here we explore the sensitivity limits of multidimensional electronic spectroscopy. We present a fluorescencedetected multidimensional electronic spectrometer based on a visible white-light continuum. As a demonstration of sensitivity, we report room temperature two-dimensional coherence maps of vibrational quantum coherences in a laser dye at optical densities ∼2-3 orders of magnitude lower than conventional approaches. This high sensitivity is enabled by a combination of biased sampling along the optical coherence time axes and a rapid scan of the waiting time T dimension at each time step. A combination of acousto-optic phase modulation and phase-sensitive lock-in detection enables simultaneous collection of rephasing and non-rephasing signals and measurements of room temperature vibrational wavepackets even at the lowest ODs. Alternative faster data collection schemes, enabled by the flexibility of continuous pump-probe scanning approach, are also demonstrated.

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Phase-modulated rapid-scanning fluorescence-detected two-dimensional electronic spectroscopy

Cited by 21 publications

References 32 publications

High-resolution two-dimensional electronic spectroscopy reveals the homogeneous line profile of chromophores solvated in nanoclusters

High-resolution two-dimensional electronic spectroscopy reveals the homogeneous line profile of chromophores solvated in nanoclusters

Equation-of-Motion Methods for the Calculation of Femtosecond Time-Resolved 4-Wave-Mixing and N-Wave-Mixing Signals

High-sensitivity Fluorescence-Detected Multidimensional Electronic Spectroscopy Through Continuous Pump-probe Delay Scan

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