β‐Carotene Revisited by Transient Absorption and Stimulated Raman Spectroscopy

Quick, Martin; Kasper, Marc‐André; Richter, Celin; Mahrwald, Rainer; Dobryakov, A. L.; Kovalenko, Sergey A.; Érnsting, N. P.

doi:10.1002/cphc.201500586

Cited by 19 publications

(18 citation statements)

References 69 publications

(199 reference statements)

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“…Since the first report by Yoshizawa et al . in 2002, an enormous amount of work has contributed to our understanding of carotene's unique excited‐state dynamics . Recent reviews on carotenes and biopolyenes have been given by Hashimoto et al .…”

Section: Systems and Applicationsmentioning

confidence: 99%

Femtosecond Stimulated Raman Spectroscopy

2016

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Femtosecond stimulated Raman spectroscopy (FSRS) is an ultrafast nonlinear optical technique that provides vibrational structural information with high temporal (sub-50 fs) precision and high spectral (10 cm(-1) ) resolution. Since the first full demonstration of its capabilities ≈15 years ago, FSRS has evolved into a mature technique, giving deep insights into chemical and biochemical reaction dynamics that would be inaccessible with any other technique. It is now being routinely applied to virtually all possible photochemical reactions and systems spanning from single molecules in solution to thin films, bulk crystals and macromolecular proteins. This review starts with an historic overview and discusses the theoretical and experimental concepts behind this technology. Emphasis is put on the current state-of-the-art experimental realization and several variations of FSRS that have been developed. The unique capabilities of FSRS are illustrated through a comprehensive presentation of experiments to date followed by prospects.

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Section: Systems and Applicationsmentioning

confidence: 99%

Femtosecond Stimulated Raman Spectroscopy

2016

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“…Transient stimulated Raman spectra of the sample are obtained by scanning the time delay between the stimulated Raman probe pair and the actinic pump pulses, where all the kinetic and structural information on the sample in the excited states is contained. The FSRS has been widely used to investigate many chemical and biological systems including reaction dynamics, vision process, and photosynthesis. ,− …”

Section: Introductionmentioning

confidence: 99%

Ultrafast Intramolecular Proton Transfer of Alizarin Investigated by Femtosecond Stimulated Raman Spectroscopy

et al. 2017

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We report time-resolved stimulated Raman spectra of alizarin in DMSO solution with 403 nm excitation. Upon photoexcitation, the intramolecular proton transfer reaction of alizarin occurs in 70-80 fs, which is confirmed by both the population growth and the frequency and bandwidth changes of skeletal vibrational modes of alizarin. Interestingly, the vibrational frequencies of ν(C═C) and ν(C═O) show opposite shifts during the reaction, which may implicate changes in the resonance structure of anthraquinone and the attached carbonyl group. Vibrational relaxation in the potential surface of the proton transferred tautomer of alizarin and the population decay occurring with two distinct time scales were also observed in addition to the solvation dynamics of DMSO solvent molecules.

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“…This was later drawn into question, based on experiments showing different temperature dependence of S* and S 1 , which is unexpected for photoinitiated excited state isomerization . The finding that S* can be “frozen out” is central to the so-called inhomogeneous ground state model, in which S 1 and S* are both first electronic excited singlet states, but of different molecular species, represented by isomers with altered end group rotation. − An alternative interpretation of pump–probe − and pump-degenerate four wave mixing data , explains S*-related features by a vibrationally hot ground state, hot S 0 . Within this hypothesis, it is important to differentiate two distinct mechanisms of addressing hot S 0 .…”

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confidence: 99%

A Unified Picture of S* in Carotenoids

Balevičius

Abramavičius

Polı́vka

et al. 2016

J. Phys. Chem. Lett.

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In π-conjugated chain molecules such as carotenoids, coupling between electronic and vibrational degrees of freedom is of central importance. It governs both dynamic and static properties, such as the time scales of excited state relaxation as well as absorption spectra. In this work, we treat vibronic dynamics in carotenoids on four electronic states (|S0⟩, |S1⟩, |S2⟩, and |Sn⟩) in a physically rigorous framework. This model explains all features previously associated with the intensely debated S* state. Besides successfully fitting transient absorption data of a zeaxanthin homologue, this model also accounts for previous results from global target analysis and chain length-dependent studies. Additionally, we are able to incorporate findings from pump-deplete-probe experiments, which were incompatible to any pre-existing model. Thus, we present the first comprehensive and unified interpretation of S*-related features, explaining them by vibronic transitions on either S1, S0, or both, depending on the chain length of the investigated carotenoid.

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β‐Carotene Revisited by Transient Absorption and Stimulated Raman Spectroscopy

Cited by 19 publications

References 69 publications

Femtosecond Stimulated Raman Spectroscopy

Femtosecond Stimulated Raman Spectroscopy

Ultrafast Intramolecular Proton Transfer of Alizarin Investigated by Femtosecond Stimulated Raman Spectroscopy

A Unified Picture of S* in Carotenoids

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