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Research on materials facilitating efficient singlet fission (SF) is driven by a possible reduction of thermalization losses in organic photovoltaic devices. Intramolecular SF (iSF) is in this context of special interest, as the targeted modification of either chromophores or linkers enables gradual variations of molecular properties. In this combined synthetic, spectroscopic, and computational work, we present and investigate nine novel spiro-linked azaarene dimers, which undergo efficient iSF with triplet yields up to 199%. Additional molecular braces enhance the rigidity of these tailor-made dimers (TMDs), resulting in great agreement between crystal structures and predicted optimal geometries for iSF in solution. Regardless of the employed chromophores and linkages, the dynamics of all nine TMDs are perfectly described by a unified kinetic model. Most notably, an increase in the orbital overlap of the π-systems by decreasing the twist angle between the two chromophores does not only increase the rate of formation of the correlated triplet pair but also further promotes its decorrelation. This new structure-function relationship represents a promising strategy toward TMDs with high triplet lifetimes to be utilized in optoelectronic devices.

Small-molecule fluorophores enable the observation of biomolecules in their native context with fluorescence microscopy. Specific labeling via bio-orthogonal tetrazine chemistry combines minimal label size with rapid labeling kinetics. At the same time, fluorogenic tetrazine–dye conjugates exhibit efficient quenching of dyes prior to target binding. However, live-cell compatible long-wavelength fluorophores with strong fluorogenicity have been difficult to realize. Here, we report close proximity tetrazine–dye conjugates with minimal distance between tetrazine and the fluorophore. Two synthetic routes give access to a series of cell-permeable and -impermeable dyes including highly fluorogenic far-red emitting derivatives with electron exchange as the dominant excited-state quenching mechanism. We demonstrate their potential for live-cell imaging in combination with unnatural amino acids, wash-free multicolor and super-resolution STED, and SOFI imaging. These dyes pave the way for advanced fluorescence imaging of biomolecules with minimal label size., This work presents probes that turn fluorescent upon specific chemical reactions in biological environments, which are highly beneficial for signal improvement in fluorescence microscopy.

Organic photovoltaics (OPVs) hold promise for a cost-effective, eco-friendly, and sustainable technology to harvest solar energy. However, the widespread application of OPVs has been hindered mostl...

Charge carrier multiplication via singlet fission into two triplet states has the potential to increase efficiencies of photovoltaics by one-third due to the reduction of thermalization losses. In the present work, we investigate tetraazaperopyrenes, a class of N-heteropolycyles, as suitable singlet fission candidates. Using a combined experimental and theoretical approach, fundamentally different mechanisms for triplet formation in solution and thin film are identified. In solution, an ultrafast intersystem crossing process is observed, which is accelerated for heavier halide substituents not only due to enhanced spin-orbit coupling but also due to the energy tuning between the S1 and T2 states. In thin films, a correlated triplet pair is formed coherently upon photoexcitation. Subsequently, an excimer formation is observed, which competes with the electronic decorrelation of the triplet pair. The comparison with peropyrene shows that aza-substitutions within the aromatic core can be a powerful strategy for tuning the energy levels of the states important to singlet fission.

In this work, we investigated energy transfer dynamics in water-dispersed polymeric nanoparticles (NPs) of F8T2, MDMO-PPV, and their mixtures (bicomponent) synthesized by the miniemulsion technique, using femtosecond transient absorption and time-resolved fluorescence spectroscopy.

Compression, shaping and characterization of broadband mid-infrared (MIR) pulses based on an acousto-optic modulator (AOM) pulse shaper is presented. Characterization of the spectral phase is achieved by an AOM-shaper based implementation of a dispersion scan (d-scan). The abilities of the setup are demonstrated by imprinting several test phases with increasing complexity on broadband MIR pulses centered at 3.2 µm and retrieval of the imprinted phases with the presented d-scan method. Phase characterization with d-scan in combination with an evolutionary algorithm allows us to compress the MIR pulses below 50 fs FWHM autocorrelation after the shaper.

Quantum chemistry and time-resolved spectroscopy are applied to rationalize how singlet fission (SF) is affected by systematic chemical modifications introduced into phenazinothiadiazoles (PTD). Substitution of the terminal aromatic ring of TIPS-tetracene by a thiadiazole group leads to a considerable change in the relative energies of its S1 and T1 states. Thus, in contrast to TIPS-tetracene, SF becomes exothermic for various PTD derivatives, which show S1-2T1 energy differences as high as 0.15 eV. This enables SF in PTD as corroborated by femtosecond transient absorption spectroscopy and TD-DFT calculations. The latter report T-T spectra consistent with thin film UV-vis femtosecond transient absorption of PTDs at long delays. TD-DFT calculations also show that the S1-T1 energy gap can be rationally tuned by introducing N atoms into the aromatic scaffold and by the halogenation of one side ring of the PTD. In addition, the specific S1-to-1(T1T1) electronic coupling depends on the crystal morphology and the electronic properties simultaneously. Thus, both of them govern the strength and the interplay between direct and superexchange couplings, which in the most favorable cases accelerate SF to rate constants beyond (100 fs)-1. Remarkably, direct coupling was found to contribute considerably to the total effective coupling and even to dominate it for some PTDs investigated here. A quantum yield of 200% is obtained on the early picosecond time scale for all compounds studied here, which is reduced to 100% due to triplet-triplet annihilation after a few nanoseconds.

Flexible shaping and phase characterization of ultrashort pulses in the mid-infrared (MIR) are still challenging. Particularly phase retrieval by, e.g., dispersion scan (d-scan) [1] is not easily implemented in the MIR. In this work, we demonstrate ultrashort pulse generation, tailoring and phase retrieval in a shaper-assisted setup. D-scan is easily implemented by applying and scanning a dispersive phase with a Germanium acousto-optic modulator (AOM)-shaper, instead of glass wedges and chirped mirrors, which are typically used in the VIS/NIR. With this setup, we can not only characterize the MIR pulse, but virtually imprint any phase on it at the same time.

International audience; La photo-isomérisation sub-picoseconde est la principale réaction initiant la conversion d’énergie dans les protéines de rétinal, si bien qu’elle fait l’objet de travaux théoriques et expérimentaux approfondis depuis plus de trente ans. Dans cet article de revue, nous revisitons la question toujours ouverte de savoir comment la protéine détermine la vitesse d’isomérisation et son rendement quantique. A la lumière de nos contributions récentes en ce domaine, nous décrivons le concept d’un mélange d’états excités réactifs et non-réactifs, délicatement ajusté par les interactions stériques et électrostatiques avec l’environnement protéique. De nouvelles perspectives et approches prometteuses sont décrites qui pourront faire progresser la compréhension de ces systèmes chromophore–protéine intimement couplés.

International audience; The introduction of N-heterocyclic carbene ligands has greatly increased the lifetimes of metal-to-ligand charge transfer states (MLCT) in iron(II) complexes, making them promising candidates for photocatalytic applications. However, the spectrally elusive triplet metal-centered state (3MC) has been suggested to play a decisive role in the relaxation of the MLCT manifold to the ground state, shortening their lifetimes and consequently limiting the application potential. In this work, time-resolved vibrational spectroscopy and quantum chemical calculations are applied to shed light on the 3MCs’ involvement in the deactivation of the MLCT manifold of an iron(II) sensitizer. Two distinct symmetric Fe–L breathing vibrations at frequencies below 150 cm–1 are assigned to the 3MC and 3MLCT states by quantum chemical calculations. On the basis of this assignment, an ultrafast branching directly after excitation forms not only the long-lived 3MLCT but also the 3MC as an additional loss channel.

Sub-picosecond photo-isomerization is the major primary process of energy conversion in retinal proteins and has as such been in the focus of extensive theoretical and experimental work over the past decades. In this review article, we revisit the long-standing question as to how the protein tunes the isomerization speed and quantum yield. We focus on our recent contributions to this field, which underscore the concept of a delicate mixing of reactive and non-reactive excited states, as a result of steric properties and electrostatic interactions with the protein environment. Further avenues and new approaches are outlined which hold promise for advancing our understanding of these intimately coupled chromophore-protein systems.

As narrow optical bandgap materials, semiconducting single-walled carbon nanotubes (SWCNTs) are rarely regarded as charge donors in photoinduced charge-transfer (PCT) reactions. However, the unique band structure and unusual exciton dynamics of SWCNTs add more possibilities to the classical PCT mechanism. In this work, we demonstrate PCT from photoexcited semiconducting (6,5) SWCNTs to a wide-bandgap wrapping poly-[(9,9-dioctylfluorenyl-2,7-diyl)-alt-(6,6′)-(2,2′-bipyridine)] (PFO–BPy) via femtosecond transient absorption spectroscopy. By monitoring the spectral dynamics of the SWCNT polaron, we show that charge transfer from photoexcited SWCNTs to PFO–BPy can be driven not only by the energetically favorable E$_{33}$ transition but also by the energetically unfavorable E$_{22}$ excitation under high pump fluence. This unusual PCT from narrow-bandgap SWCNTs toward a wide-bandgap polymer originates from the up-converted high-energy excitonic state (E$_{33}$ or higher) that is promoted by the Auger recombination of excitons and charge carriers in SWCNTs. These insights provide new pathways for charge separation in SWCNT-based photodetectors and photovoltaic cells.

Singlet fission (SF) is a process by which one excited singlet state yields two triplet states upon close interaction with a ground-state chromophore of the same kind. This photoreaction was first observed in solid state and has important implications in organic photovoltaics. Singlet fission was also reported in concentrated solutions, where the need for diffusion of the reaction partners slows the dynamics. This helps to single out reaction stages and to identify the involved species. In this work, ultrafast transient absorption spectroscopy and time-correlated single photon counting are applied to the concentration-dependent (from 10-1 to 102 mM) photodynamics of a tetrachlorinated phenazinothiadiazole in toluene. Time-resolved emission shows a monoexponential decay, which is constant across the emission band. The corresponding decay rate depends linearly on the concentration of the phenazinothiadiazole. Femtosecond transient absorption demonstrates that a concentration-dependent singlet-to-triplet conversion hides behind the emission decay which is diffusion controlled. Contrary to previous reports on SF in pentacenes and tetracenes, no indication of intermediate states has been found. Efficient, direct and barrierless SF is concluded. The strong enhancement of the triplet yield at increasingly higher concentrations of the thiadiazole indicates very efficient singlet fission with a triplet yield up to 189 ± 5%.

Singlet fission (SF) has the potential to boost solar energy conversion. Research has focused on designing new strategies to tune the electrochemistry, photophysics, and device architecture at the molecular level to improve the efficiency of SF sensitizers. These studies indicate that SF efficiency strongly depends on morphology, packing, and chemical structure. In this work, we use time-resolved spectroscopy to study intramolecular SF in three covalently linked azaarene dimers. Their rigid structure makes them promising model systems to investigate the effect of chemical modification on intramolecular SF without any potential contributions from geometrical factors. Our experimental results along with theoretical calculations show that SF occurs in all three dimers, confirming SF in perpendicularly oriented chromophores with negligible overlapping π-systems. Additionally, a complex branching mechanism is discovered for the evolution of the singlet (S0S1) and the correlated triplet pair 1(T1T1) states. Although chemical modification has only a minor effect on SF rate and generation of the correlated triplet pair, it plays a critical role in the evolution toward the formation of free triplets. Finally, comparison of deaerated and aerated solutions underpins the effect of oxygen in altering the 1(T1T1) dynamics by opening new decay pathways.

Singlet fission (SF) has the potential to dramatically increase solar cell efficiency by converting one singlet exciton to two free triplet excitons via a correlated triplet pair intermediate. Identification and characterization of excited states involved in SF are of great importance for understanding the fundamentals of SF. Despite their importance, it is still nontrivial to distinguish various species in transient absorption spectra due to their spectral overlaps and ultrashort lifetimes. Theoretical modeling of SF and its electronically excited state absorption (ESA) is generally challenging due to the multiexciton nature of the correlated triplet pair, which usually requires description by expensive high-level ab initio methods. In this work, taking the bis((triisopropylsilyl)ethynyl) (TIPS)-pentacene monomer and its covalently linked dimer as representative examples, we demonstrate the use of single-reference DFT-based approaches to simulate the ESA spectra during SF. In particular, the singlet and triplet ESA are evaluated by TDDFT, QR-TDDFT, SLR-TDDFT, SF-TDDFT, and UTDDFT, in combination with ten different exchange-correlation functionals. The correlated triplet pair and its ESA are characterized by broken-symmetry DFT and TDDFT, and the role of orbital relaxation is highlighted. With a rational choice of exchange-correlation functionals, we found the resulting spectra to show good agreement with transient absorption experiments and certain improvements over high-order CI methods.

Small-molecule fluorophores enable the observation of biomolecules in their native context with fluorescence microscopy. Specific labelling via bioorthogonal tetrazine chemistry confers minimal label size and rapid labelling kinetics. At the same time, fluorogenic tetrazine-dye conjugates exhibit efficient quenching of dyes prior to target binding. However, live-cell compatible long-wavelength fluorophores with strong fluorogenicity have been difficult to realize. Here, we report close proximity tetrazine-dye conjugates with minimal distance between tetrazine and fluorophore. Two synthetic routes give access to a series of cell permeable and impermeable dyes including highly fluorogenic far-red emitting derivatives with electron exchange as dominant excited state quenching mechanism. We demonstrate their potential for live-cell imaging in combination with unnatural amino acids, wash-free multi-colour and super-resolution STED and SOFI imaging. These dyes pave the way for advanced fluorescence imaging of biomolecules with minimal label size.

Time-resolved spectroscopies have been playing an essential role in the elucidation of the fundamental mechanisms of light-driven processes, particularly in exploring relaxation models for electronically excited molecules. However, the determination of such models from experimentally obtained time-resolved and spectrally resolved data still demands a high degree of intuition, frequently poses numerical challenges, and is often not free from ambiguities. Here, we demonstrate the analysis of time-resolved laser spectroscopy data via a deep learning network to obtain the correct relaxation kinetic model. In its current design, the presented Deep Spectroscopy Kinetic Analysis Network (DeepSKAN) can predict kinetic models (involved states and relaxation pathways) consisting of up to five states, which results in 103 possible different classes, by estimating the probability of occurrence of a given kinetic model class. DeepSKAN was trained with synthetic time-resolved spectra spanning over 4 orders of magnitude in time with a unitless time axis, thereby demonstrating its potential as a universal approach for analyzing data from various time-resolved spectroscopy techniques in different time ranges. By adding the probabilities of each pathway of the top

Deoxyuridine nucleosides embodied into diarylethenes form an especial class of photoswitchable compounds that are designed to stack and pair with DNA bases. The molecular geometry can be switched between "open" and "closed" isomers by a pericyclic reaction that affects the stability of the surrounding double helix. This potentially enables light-induced control of DNA hybridization at microscopic resolution. Despite its importance for the optimization of DNA photoswitches, the ultrafast photoisomerization mechanism of these diarylethenes is still not well understood. In this work, femtosecond transient absorption spectroscopy is applied to study the ring closing reaction upon UV excitation with 45 fs pulses. Excited-state absorption decays rapidly and gives rise to the UV-Vis difference spectrum of the "closed" form within ≈15 ps. Time constants of 0.09, 0.49 and 6.6 ps characterize the multimodal dynamics, where a swift recurrence in the signal anisotropy indicates transient population of the intermediate 21A-like state.

Discrepancies in the isomerization dynamics and quantum yields of the trans and cis retinal protonated Schiff base is a well-known issue in the context of retinal photochemistry. Anabaena Sensory Rhodopsin (ASR) is a microbial retinal protein that comprises a retinal chromophore in two ground state (GS) conformations: all-trans, 15-anti (AT) and 13-cis, 15-syn (13C). In this study, we applied impulsive vibrational spectroscopic techniques (DFWM, pump-DFWM and pump-IVS) to ASR to shed more light on how the structural changes take place in the excited state within the same protein environment. Our findings point to distinct features in the ground state structural conformations as well as to drastically different evolutions in the excited state manifold. The ground state vibrational spectra show stronger Raman activity of the C14-H out-of-plane wag (at about 805 cm-1) for the 13C isomer than that for the AT isomer, which hints at a pre-distortion of 13C in the ground state. Evolution of the Raman frequency after interaction with the actinic pulse shows a blue-shift for the C[double bond, length as m-dash]C stretching and CH3 rocking mode for both isomers. For AT, however, the blue-shift is not instantaneous as observed for the 13C isomer, rather it takes more than 200 fs to reach the maximum frequency shift. This frequency blue-shift is rationalized by a decrease in the effective conjugation length during the isomerization reaction, which further confirms a slower formation of the twisted state for the AT isomer and corroborates the presence of a barrier in the excited state trajectory previously predicted by quantum chemical calculations.

Spectral phase characterization of ultrashort laser pulses is essential in nonlinear micro-spectroscopy. Whereas in many applications phases are determined for near-infrared (NIR) pulses, successful mid-infrared (MIR) phase retrieval is rare. The spectral phase of ultra-broadband MIR pulses is determined over more than 1000 c m − 1 in the presented work. This is accomplished by exploiting the d-scan method in two variants. Both allow for detecting high signals by using the interaction of the MIR and NIR pulses. The two variants differ in imprinting the dispersion. While the dual d-scan imprints phases on both pulses, the Xd-scan method disperses the NIR pulses solely.

Generating two long-living low-energy excitations after absorption of a single high-energy photon has stoked interest in singlet fission (SF) to enhance solar energy conversion in photovoltaics. To this end, survival of the triplet states is critical. This process is investigated in diethynylbenzene-linked tetraaza-triisopropylsilylethynyl-pentacene dimers, for which SF is energetically feasible and facilitated by the close distances between the azapentacenes. The

Singlet fission is the photoinduced conversion of a singlet exciton into two triplet states of half-energy. This multiplication mechanism has been successfully applied to improve the efficiency of single-junction solar cells in the visible spectral range. Here we show that singlet fission may also occur via a sequential mechanism, where the two triplet states are generated consecutively by exploiting oxygen as a catalyst. This sequential formation of carriers is demonstrated for two acene-like molecules in solution. First, energy transfer from the excited acene to triplet oxygen yields one triplet acene and singlet oxygen. In the second stage, singlet oxygen combines with a ground-state acene to complete singlet fission. This yields a second triplet molecule. The sequential mechanism accounts for approximately 40% of the triplet quantum yield in the studied molecules; this process occurs in dilute solutions and under atmospheric conditions, where the single-step SF mechanism is inactive., Singlet fission is a promising carrier multiplication process, where a singlet exciton is split in two triplet states. Here the authors propose an oxygen-assisted two-step mechanism for singlet fission accounting for ~ 40% triplet quantum yield in dilute solutions where the single-step mechanism is inactive.

Spectroscopy methods including mid-infrared (MIR)-, coherent anti-Stokes Raman scattering (CARS)-, two photon excitation fluorescence (TPEF), second harmonic generation (SHG)- and sum frequency generation (SFG) microscopy are versatile analytical tools in life and material sciences [1]. Pathing the way for the development of an all-purpose laser excitation tool for multimodal microscopy, a vibrational resonant sum frequency (SF) spectroscopy technique is implemented in two approaches: a homodyne mid-infrared scanning and a heterodyne multiplexing scheme. This setup, which is already capable of TPEF, SHG, CARS and MIR microscopy [2], uses the flexibility of a programmable pulse shaper to shape the sub 10 fs near-infrared laser pulses. The pulse shaping provides in both approaches the spectral resolution by use of either Spectral Focusing [3] for monochromatic MIR light generation in the homodyne scanning mode or Double Quadrature Spectral Interferometry [4] for heterodyne amplified SF-signal generation in the multiplex mode.

The light induced isomerization of retinal protonated Schiff base (RPSB) inside the protein pocket is one of the fastest (

The interaction between the retinal protonated Schiff base (RPSB) and surrounding protein residues inside the retinal pocket is believed to play a major role in the ultrafast isomerization of the former. Coherent time-resolved vibrational spectroscopic techniques are applied to reveal the effect of changes in the protein architecture by point mutations (V112N and L83Q) close to the RPSB in Anabaena sensory rhodopsin (ASR). Our study reveals that such point mutations have a minor effect on the low-frequency (

Ultrafast transient absorption and quantum chemistry calculations are combined to demonstrate singlet fission in newly functionalized TIPS-Tetracenes. The coupling strength (but not the energy gap) between Si and ’(TT) states gauges singlet fission efficiency and rate.

Singlet fission is slowed down on diffusional timescales in highly concentrated solutions compared to thin films for a tetracene-like molecule. The underlying mechanism suggests competing intersystem crossing and singlet fission, where in the latter singlets are converted directly to triplets without an intermediate excimer state.

International audience

The ultrafast structural changes during the photoinduced isomerization of the retinal-protonated Schiff base (RPSB) is still a poorly understood aspect in the retinal's photochemistry. In this work, we apply pump-degenerate four-wave mixing (pump-DFWM) to all- trans retinal (ATR) and retinal Schiff bases (RSB) to resolve coherent high- and low-frequency vibrational signatures from excited electronic states. We show that the vibrational spectra of excited singlet states in these samples exhibit pronounced differences compared to the relaxed ground state. Pump-DFWM results indicate three major features for ATR and RSB. (i) Excited state vibrational spectra of ATR and RSB consist predominately of low-frequency modes in the energetic range 100-500 cm-1. (ii) Excited state vibrational spectra show distinct differences for excitation in specific regions of electronic transitions of excited state absorption and emission. (iii) Low-frequency modes in ATR and RSB are inducible during the entire lifetime of the excited electronic states. This latter effect points to a transient molecular structure that, following initial relaxation between different excited electronic states, does not change anymore over the lifetime of the finally populated excited electronic state.

The light-activated cleavage of cyclobutane-based systems via [2 + 2] cycloreversions, such as thymine and coumarin dimers, is an important but still poorly understood ultrafast photochemical reaction. Systems displaying reversible cycloreversion have found various uses in cross-linked polymers, enhancing gas adsorption affinities in inorganics, and light-activated medical therapies. We report the identification of a heterogeneous mode of cycloreversion for a rarely examined coumarin analogue system. Quinolinone monomers and dimers were probed using ultraviolet pumped, transient absorption spectroscopy and demonstrated radically different photophysical properties than coumarins. Monomers displayed enhanced intersystem crossing at almost 1:1 versus the combined nonradiative and radiative singlet decay, while the dimers underwent cycloreversion to a one excited-one ground state monomer photoproduct pair. The change in both systems was directly linked to the lactame group in the quinolinone motif. This discovery highlights the dramatic effects that small chemical changes can have on photoreaction pathways and opens up a new means to produce and develop more efficient cycloaddition-cycloreversion systems.

The field of multidimensional laser spectroscopy comprises a variety of highly developed state-of-the-art methods, which exhibit broad prospects for applications in several areas of natural, material, and even medical sciences. This collection summarizes the main achievements from this area and gives basic introductory insight into what is currently possible with such methods. In the present introductory contribution, we briefly outline the general concept behind multidimensional laser spectroscopy, for instance by highlighting the often-employed analogy between multidimensional laser spectroscopy and NMR methods. Our initial introduction is followed by an overview of the most important and widely used multidimensional spectroscopies' classification. Special emphasis is placed on how the contributing spectral region defines a natural way of grouping the techniques in terms of their information content. On this basis, we introduce the most important graphical ways in which multidimensional data is generally visualized. This is done by comparing specifically temporal and spectra axes that make up each single multidimensional data plot. Several central experimental methods that are common to the various techniques reviewed in this collection are addressed in the perspective of recent developments and their impact on the field. These methods include, for example, heterodyne/homodyne detection, fast scanning, spatial light modulation, and sparse sampling methods. Importantly, we address the central and fundamental questions where multidimensional ultrafast spectroscopy can be used to help understanding chemical dynamics and intermolecular interactions. Finally, we briefly pinpoint what we believe are the main open questions and what will be the future directions for technical developments and promotion of scientific understanding that multidimensional spectroscopy can provide for chemistry, physics, and life sciences.

Mechanisms and optimal experimental conditions in coherent control still intensely stimulate debates. In this work, a phase-only control mechanism in an open quantum system is investigated experimentally and numerically. Several parameterizations for femtosecond pulse shaping (combination of chirp and multipulses) are exploited in transient absorption of a prototype organic molecule to control population and vibrational coherence in ground and excited states. Experimental results are further numerically simulated and corroborated with a four-level density-matrix model, which reveals a phase-only control mechanism based on the interaction between the tailored phase of the excitation pulse and the induced transient absorption. In spite of performing experiment and numerical simulations in the linear regime of excitation, the control effect amplitude depends non-linearly on the excitation energy and is explained as a pump-dump control mechanism. No evidence of single-photon control is observed with the model. Moreover, our results also show that the control effect on the population and vibrational coherence is highly dependent on the spectral detuning of the excitation spectrum. Contrary to the popular belief in coherent control experiments, spectrally resonant tailored excitation will lead to the control of the excited state only for very specific conditions.

International audience; Anabaena Sensory Rhodopsin is a particular microbial retinal protein for which light-adaptation leads to the ability to bind both the all-trans, 15-anti (AT) and the 13-cis, 15-syn (13C) isomers of the protonated Schiff base of retinal (PSBR). In the context of obtaining insight into the mechanisms by which retinal proteins catalyse the PSBR photo-isomerization reaction, ASR is a model system allowing to study, within the same protein, the protein-PSBR interactions for two different PSBR conformers at the same time. A detailed analysis of the vibrational spectra of AT and 13C, and their photo-products in wild-type ASR obtained through femtosecond (pump-) four-wave-mixing is reported for the first time, and compared to bacterio-and channelrhodopsin. As part of an extensive study of ASR mutants with blue-shifted absorption spectra, we present here a detailed computational analysis of the origin of the mutation-induced blue-shift of the absorption spetra, and identify electrostatic interactions as dominating steric effects that would entail a red-shift. The excited state lifetimes and isomerization reaction times (IRT) for the three mutants V112N, W76F, and L83Q are studied experimentally by femtosecond broadband transient absorption spectroscopy. Interestingly, in all three mutants, isomerization is accelerated for AT with respect to wild-type ASR, and this the more, the shorter the wavelength of maximum absorption. On the contrary, the 13C photo-reaction is slightly slowed down, leading to an inversion of the ESLs of AT and 13C, with respect to wt-ASR, in the blue-most absorbing mutant L83Q. Possible mechanisms for these mutation effects, and their steric and electrostatic origins are discussed.

Controlling chemical reactions by light, i.e., the selective making and breaking of chemical bonds in a desired way with strong-field lasers, is a long-held dream in science. An essential step toward achieving this goal is to understand the interactions of atomic and molecular systems with intense laser light. The main focus of experiments that were performed thus far was on quantum-state population changes. Phase-shaped laser pulses were used to control the population of final states, also, by making use of quantum interference of different pathways. However, the quantum-mechanical phase of these final states, governing the system's response and thus the subsequent temporal evolution and dynamics of the system, was not systematically analyzed. Here, we demonstrate a generalized phase-control concept for complex systems in the liquid phase. In this scheme, the intensity of a control laser pulse acts as a control knob to manipulate the quantum-mechanical phase evolution of excited states. This control manifests itself in the phase of the molecule's dipole response accessible via its absorption spectrum. As reported here, the shape of a broad molecular absorption band is significantly modified for laser pulse intensities ranging from the weak perturbative to the strong-field regime. This generalized phase-control concept provides a powerful tool to interpret and understand the strong-field dynamics and control of large molecules in external pulsed laser fields.

Die Prozessierung organischer Bauelemente aus der Flussigphase ist ein wichtiger Schritt zur Entwicklung kostengunstiger Fertigungsprozesse. Wir beschreiben eine Methode zur lichtinduzierten Loslichkeitsschaltung eines π-konjugierten Polymers (Polyfluoren), dessen Seitenketten mit Hydroxyzimtsaureester funktionalisiert sind. Die Belichtung dunner Polymerfilme fuhrt zur Abspaltung der Seitenketten, wodurch die Loslichkeit der Filme drastisch gesenkt wird. In einer ersten Konzeptstudie wurden die synthetisierten Polyfluorene als Emittermaterialien in OLEDs eingesetzt. Belichtung der Emitterschicht fuhrt auser der Loslichkeitsschaltung auch zu einem deutlichen Leistungsanstieg der OLED. Dieser Befund eroffnet die Moglichkeit zur gezielten Manipulation der Loslichkeit und der Emissionseigenschaften einer wichtigen Klasse funktioneller Materialien.

Femtosecond pump-depletion-probe experiments were carried out in order to shed light on the ultrafast excited-state dynamics of triisopropylsilylethynyl (TIPS)-pentacene and two nitrogen-containing derivatives, namely, diaza-TIPS-pentacene and tetraaza-TIPS-pentacene. Measurements performed in the visible and near-infrared spectral range in combination with rate model simulations reveal that singlet fission proceeds via the extremely short-lived intermediate (1)TT state, which absorbs in the near-infrared spectral region only. The T1 → T3 transition probed in the visible region shows a rise time that comprises two components according to a consecutive reaction (S1 → (1)TT → T1). The incorporation of nitrogen atoms into the acene structure leads to shorter dynamics, but the overall triplet formation follows the same kinetic model. This is of particular importance, since experiments on tetraaza-TIPS-pentacene allow for investigation of the triplet state in the visible range without an overlapping singlet contribution. In addition, the pump-depletion-probe experiments show that the triplet absorption in the visible (T1 → T3) and near-infrared (T1 → T2) regions occurs from the same initial state, which was questioned in previous studies. Furthermore, an additional ultrafast transfer between the excited triplet states (T3 → T2) is identified, which is also in agreement with the rate model simulation. By applying depletion pulses, which are resonant with higher vibrational levels, we gain insight into internal vibrational energy redistribution processes within the triplet manifold. This additional information is of great relevance regarding the study of loss channels within these materials.

A novel scheme for the detection of known species with single-beam coherent anti-Stokes Raman scattering spectroscopy is presented in theory and simulations. The introduction of a simulation tool based on fast Fourier transforms allows a purely numerical optimization of excitation phases ex situ, to which we refer to as in silico optimization. Such an optimal phase is based on the encoding of vibrational resonances in specific spectral detection windows using multichannel measurements. The presented detection scheme offers a route to fast chemical selective imaging with high contrast and simplified data acquisition, thereby avoiding photodamage of sensitive biological samples. Copyright © 2015 John Wiley & Sons, Ltd.

Liquid-crystal spatial light modulators (LCM) are a common tool to tailor femtosecond laser pulses. The phase stability of 1 kHz, sub-20 fs visible shaped and unshaped pulses are investigated. Our results show that the spectral phase after the LCM varies from pulse to pulse leading to strong deviations from the predicted pulse shapes. This phase instability is generated only by LCM and is strongly temperature dependent. Based on the experimental data, a numerical model for the phase was developed that takes the temperature-dependent phase instability as well as pixel coupling across the LCM into account. Phase stability after the LCM can be improved by an order of magnitude by combining the control the temperature of the LCM and by using rapid-scan averaging. Reliable pulse shapes on a pulse-to-pulse basis are crucial, especially in coherent control experiments, where small differences between pulse shape are important.

The complexity of experimental schemes still challenges the broad application of multimodal microscopy beyond fundamental research. Pulse shaping has been a promising candidate to assist in the implementation of flexible and compact schemes. In this work, its application is demonstrated for vibrational resonant sum frequency (SF) spectroscopy in a nonlinear Raman microscope. The mixing of an ultrabroadband NIR laser pulse with a difference-frequency-generated MIR spectrum provides spectral access from 1750 c m − 1 to beyond 3000 c m − 1 via two shaping methods: (i) homodyne MIR scanning and (ii) heterodyne multiplex. The versatility of shaper-based SF is demonstrated in the spectroscopy and microscopy of crystalline cholesterol and cysteine.

The ground and excited state evolution of fingerprint vibrational modes of all-trans-and 13-cis-retinal are mapped by impulsive vibrational spectroscopy. All-trans-retinal shows slower frequency shift dynamics in the excited state in comparison to 13-cis-retinal.

In this report, we demonstrate how to obtain Raman spectra from single-beam CARS measurements under the condition of strong overlapping two-photon excited fluorescence (2PEF). Our approach is based on the use of a narrowband phase gate implemented via femtosecond laser pulse shaping from a single broadband laser source, without any use of polarization or amplitude modulation. The decisive quantity regarding the creation of 2PEF with shaped laser pulses is the second harmonic power spectrum, which shows a different dependence on the excitation phase from the CARS signal generation. By shifting the phase or the position of the gate in an appropriate way, it is possible to keep the second harmonic power spectrum and 2PEF constant, paving the way for an elimination of it. This allows to reconstruct the Raman signal and to retrieve quantitative information of resonances even when the fluorescence is about 160 times larger than the CARS signal. Copyright © 2013 John Wiley & Sons, Ltd.

Coherent vibrational dynamics of retinal in excited electronic states are of primary importance in the understanding of photobiology. Using pump-DFWM, we demonstrate for the first time the existence of coherent double-bond high-frequency modulations (>1300 cm(-1)) in the excited electronic state of different retinal derivatives. All-trans retinal as well as retinal Schiff bases exhibit a partial frequency downshift of the C═C double-bond mode from ∼1580 cm(-1) in the ground state to 1510 cm(-1) in the excited state. In addition, a new vibrational band at ∼1700 cm(-1) assigned to the C═N stretching mode in retinal Schiff bases in the excited state is detected. The newly reported bands are observed only in specific spectral regions of excited-state absorption. Implications regarding the observation of vibrational coherences in naturally occurring retinal protonated Schiff bases in rhodopsins are discussed.

Multiplex coherent anti-Stokes Raman scattering (MCARS) microscopy was carried out to map a solid tumor in mouse brain tissue. The border between normal and tumor tissue was visualized using support vector machines (SVM) as a higher ranking type of data classification. Training data were collected separately in both tissue types, and the image contrast is based on class affiliation of the single spectra. Color coding in the image generated by SVM is then related to pathological information instead of single spectral intensities or spectral differences within the data set. The results show good agreement with the H&E stained reference and spontaneous Raman microscopy, proving the validity of the MCARS approach in combination with SVM.

Femtosecond pump-depletion-probe experiments were carried out in order to unveil the ultrafast excited singlet fission dynamics of TIPS-pentacene derivatives. The extremely short-lived intermediate 1TT state is revealed and the nitrogen-substitution leads to shorter dynamics.

A quantum control spectroscopy (QCS) approach using directly shaped UV excitation pulse is demonstrated. Ultrafast tailored pulses in the region of 310-335 nm are combined with transient absorption to investigate reactive pathways in the excited state of (2,2'-bipyridyl)-3,3'-diol BP(OH)2. In particular, we apply QCS in the disentanglement of the competing excited-state intramolecular proton-transfer (ESIPT) channels of BP(OH)2. Our results challenge parallel reactive pathways in the excited state and suggest a newer model based on an extremely fast sequential double ESIPT process.