Facile collection of two-dimensional electronic spectra using femtosecond pulse-shaping Technology

Grumstrup, Erik M.; Shim, Sang‐Hee; Montgomery, Matthew A.; Damrauer, Niels H.; Zanni, Martin T.

doi:10.1364/oe.15.016681

Cited by 138 publications

(105 citation statements)

References 29 publications

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“…S1) using an LCD-based pulse shaper that was also used to produce the double pulses separated by coherence time τ (see scheme in upper left in Fig. 3) required for 2D spectroscopy in pump-probe geometry (36). The probe continuum (5) was generated by focusing a small portion of the 800-nm pulses into a CaF 2 plate.…”

Section: Methodsmentioning

confidence: 99%

Multidimensional spectroscopy of photoreactivity

Ruetzel¹,

Diekmann²,

Nuernberger³

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

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Coherent multidimensional electronic spectroscopy is commonly used to investigate photophysical phenomena such as light harvesting in photosynthesis in which the system returns back to its ground state after energy transfer. By contrast, we introduce multidimensional spectroscopy to study ultrafast photochemical processes in which the investigated molecule changes permanently. Exemplarily, the emergence in 2D and 3D spectra of a cross-peak between reactant and product reveals the cis-trans photoisomerization of merocyanine isomers. These compounds have applications in organic photovoltaics and optical data storage. Cross-peak oscillations originate from a vibrational wave packet in the electronically excited state of the photoproduct. This concept isolates the isomerization dynamics along different vibrational coordinates assigned by quantum-chemical calculations, and is applicable to determine chemical dynamics in complex photoreactive networks.photoreactive processes | ultrafast spectroscopy | 2D spectroscopy | vibrational coherence A basic objective of physical chemistry is to determine the mechanisms underlying chemical reactions. Fundamental insights into these are provided by femtosecond time-resolved spectroscopy, even below the timescale of molecular vibrations (1). The major challenge of ultrafast photochemistry is to identify isolated signatures of reactants, intermediates, and products, whose spectral bands often overlap. Here we show that such ambiguities are unraveled by coherent multidimensional electronic spectroscopy, e.g., 2D and 3D spectroscopy, where the correlation of a system's excitation and emission frequencies is measured separating features that otherwise superpose. We detect photoreactivity directly via cross-peaks in multidimensional spectra. This opens the broad field of femtochemistry (1) to the multidimensional concept.Two-dimensional electronic spectroscopy (2-5) was primarily implemented for studying photophysical phenomena such as energy transfer in multichromophore light-harvesting systems or other excitonically coupled systems (6-11). Recently, charge transfer has also been investigated (12, 13). Here we are interested in photochemical processes leading to ground-state product species with a molecular configuration that is different from the initial reactant. As a general extension of 2D spectroscopy, 3D representations provide an even more detailed picture. Coherent 3D spectroscopy has been introduced to infrared spectroscopy (14, 15), and recently to electronic spectroscopy for isolating excitonic coherences (16, 17), for liquid-and gas-phase model systems (18)(19)(20), and for analyzing photosynthetic lightharvesting (21,22). Regarding these approaches, one has to differentiate between fifth-order experiments (14, 15, 19) for effects of higher nonlinearity (e.g., three-point frequency-fluctuation correlation functions) (14) and third-order techniques (20)(21)(22)(23)(24), as demonstrated here to unravel photochemical reactions.The principal idea of multidimensional spectrosc...

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Section: Methodsmentioning

confidence: 99%

Multidimensional spectroscopy of photoreactivity

Ruetzel¹,

Diekmann²,

Nuernberger³

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

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“…sampling theorem. 24 A 2D Fourier transform with respect to these two delay times yields a 2D spectrum for a given population time T. Especially for gaseous samples, coherences are long-lived 25 and hence require large time delays for the two indirect dimensions. Furthermore, it may also be useful to perform an additional Fourier transform with respect to the population time T and generate a quasi-3D spectrum in order to distinguish the origin of coherences 26,27 or different channels in molecular reactions.…”

Section: Introductionmentioning

confidence: 99%

Optimizing sparse sampling for 2D electronic spectroscopy

Roeding

Klimovich

Brixner

2017

The Journal of Chemical Physics

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We present a new data acquisition concept using optimized non-uniform sampling and compressed sensing reconstruction in order to substantially decrease the acquisition times in action-based multidimensional electronic spectroscopy. For this we acquire a regularly sampled reference data set at a fixed population time and use a genetic algorithm to optimize a reduced non-uniform sampling pattern. We then apply the optimal sampling for data acquisition at all other population times. Furthermore, we show how to transform two-dimensional (2D) spectra into a joint 4D time-frequency von Neumann representation. This leads to increased sparsity compared to the Fourier domain and to improved reconstruction. We demonstrate this approach by recovering transient dynamics in the 2D spectrum of a cresyl violet sample using just 25% of the originally sampled data points.

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“…61,62 Both approaches present advantages and also limitations and technical difficulties. The heterodyne-detected three-pulse photon echo (Fig.…”

Section: Femtosecond Stimulated Raman Scatteringmentioning

confidence: 99%

“…Advantages of this configuration are its simplicity and the fact that it automatically measures absorptive 2DES spectra, which are the most direct to interpret. Collinear phase-locked pulses can be generated by a pulse shaper, such as a liquid crystal spatial light modulator, 62 an acousto-optic modulator, 61 an acoustooptic programmable dispersive filter 63 or alternatively a passive birefringent delay line. 64 …”

Section: Femtosecond Stimulated Raman Scatteringmentioning

confidence: 99%

Tracking the primary photoconversion events in rhodopsins by ultrafast optical spectroscopy

Polli

Rivalta

Nenov

et al. 2015

Photochem Photobiol Sci

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Opsins are a broad class of photoactive proteins, found in all classes of living beings from bacteria to higher animals, which work either as light-driven ion pumps or as visual pigments. The photoactive function in opsins is triggered by the ultrafast isomerization of the retinal chromophore around a specific carbon double bond, leading to a highly distorted, spectrally red-shifted photoproduct. Understanding, by either experimental or computational methods, the time course of this photoisomerization process is of utmost importance, both for its biological significance and because opsin proteins are the blueprint for molecular photoswitches. This paper focuses on the ultrafast 11-cis to all-trans isomerization in visual rhodopsins, and has a twofold goal: (i) to review the most recent experimental and computational efforts aimed at exposing the very early phases of photoconversion; and (ii) discuss future advanced experiments and calculations that will allow an even deeper understanding of the process. We present high time resolution pump-probe data, enabling us to follow the wavepacket motion through the conical intersection connecting excited and ground states, as well as femtosecond stimulated Raman scattering data allowing us to track the subsequent structural evolution until the first stable all-trans photoproduct is reached. We conclude by introducing computational results for two-dimensional electronic spectroscopy, which has the potential to provide even greater detail on the evolution of the electronic structure of retinal during the photoisomerization process.

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Facile collection of two-dimensional electronic spectra using femtosecond pulse-shaping Technology

Cited by 138 publications

References 29 publications

Multidimensional spectroscopy of photoreactivity

Multidimensional spectroscopy of photoreactivity

Optimizing sparse sampling for 2D electronic spectroscopy

Tracking the primary photoconversion events in rhodopsins by ultrafast optical spectroscopy

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