Observation of π solitons in oscillating waveguide arrays.

Floquet systems with periodically varying in time parameters enable realization of unconventional topological phases that do not exist in static systems with constant parameters and that are frequently accompanied by appearance of novel types of the topological states. Among such Floquet systems are the Su-Schrieffer-Heeger lattices with periodically-modulated couplings that can support at their edges anomalous π modes of topological origin despite the fact that the lattice spends only half of the evolution period in topologically nontrivial phase, while during other half-period it is topologically trivial. Here, using Su-Schrieffer-Heeger arrays composed from periodically oscillating waveguides inscribed in transparent nonlinear optical medium, we report experimental observation of photonic anomalous π modes residing at the edge or in the corner of the one- or two-dimensional arrays, respectively, and demonstrate a new class of topological π solitons bifurcating from such modes in the topological gap of the Floquet spectrum at high powers. π solitons reported here are strongly oscillating nonlinear Floquet states exactly reproducing their profiles after each longitudinal period of the structure. They can be dynamically stable in both one- and two-dimensional oscillating waveguide arrays, the latter ones representing the first realization of the Floquet photonic higher-order topological insulator, while localization properties of such π solitons are determined by their power.

Observation of nonlinear disclination states.

Introduction of controllable deformations into periodic materials that lead to disclinations in their structure opens novel routes for construction of higher-order topological insulators hosting topological states at disclinations. Appearance of these topological states is consistent with the bulk-disclination correspondence principle, and is due to the filling anomaly that results in fractional charges to the boundary unit cells. So far, topological disclination states were observed only in the linear regime, while the interplay between nonlinearity and topology in the systems with disclinations has been never studied experimentally. We report here on the experimental observation of the nonlinear photonic disclination states in waveguide arrays with pentagonal or heptagonal disclination cores inscribed in transparent optical medium using the fs-laser writing technique. The transition between nontopological and topological phases in such structures is controlled by the Kekulé distortion coefficient r with topological phase hosting simultaneously disclination states at the inner disclination core and spatially separated from them corner-I, corner-II, and extended edge states at the outer edge of the structure. We show that the robust nonlinear disclination states bifurcate from their linear counterparts and that location of their propagation constants in the gap and, hence, their spatial localization can be controlled by their power. Nonlinear disclination states can be efficiently excited by Gaussian input beams, but only if they are focused into the waveguides belonging to the disclination core, where such topological states reside. Our results open new prospects for investigation of nonlinear effects in topological systems with disclinations and are relevant for different areas of science, including Bose-Einstein and polariton condensates, where potentials with the disclinations can be created.

Ultrafast Energy Transfer Determines the Formation of Fluorescence in DOM and Humic Substances.

Humification is a ubiquitous natural process of biomass degradation that creates multicomponent systems of nonliving organic matter, including dissolved organic matter (DOM) and humic substances (HS) in water environments, soils, and organic rocks. Despite significant differences in molecular composition, the optical properties of DOM and HS are remarkably similar, and the reason for this remains largely unknown. Here, we employed fluorescence spectroscopy with (sub)picosecond resolution to elucidate the role of electronic interactions within DOM and HS. We revealed an ultrafast decay component with a characteristic decay lifetime of 0.5-1.5 ps and spectral diffusion originating from excitation energy transfer (EET) in the system. The rate of EET was positively correlated to the fraction of aromatic species and tightness of aromatic species packing. Diminishing the number of EET donor-acceptor pairs by reduction with NaBH4 (decrease of the acceptor number), decrease of pH (decrease of the electron-donating ability), or decrease of the average particle size by filtration (less donor-acceptor pairs within a particle) resulted in a lower impact of the ultrafast component on fluorescence decay. Our results uncover the role of electronic coupling among fluorophores in the formation of DOM and HS optical properties and provide a framework for studying photophysical processes in heterogeneous systems of natural fluorophores.

Photochemistry of hexachloroosmate(IV) in ethanol.

The photochemistry of the OsIVCl62- complex in ethanol was studied by means of stationary photolysis, nanosecond laser flash photolysis, ultrafast pump-probe spectroscopy and quantum chemistry. The direction of the photochemical process was found to be wavelength-dependent. Irradiation in the region of the d-d and LMCT bands results in the photosolvation (with the wavelength-dependent quantum yield) and photoreduction of Os(iv) to Os(iii), correspondingly. The characteristic time of photosolvation is ca. 40 ps. Photoreduction occurs in the micro- and millisecond time domains via several Os(iii) intermediates. The nature of intermediates and the possible mechanisms of photoreduction are discussed. We believe that the lability of the photochemically produced Os(iv) and Os(iii) intermediates determines the synthetic potential of OsIVCl62- photochemistry.

Fluorescence Lifetime and Intensity of Thioflavin T as Reporters of Different Fibrillation Stages: Insights Obtained from Fluorescence Up-Conversion and Particle Size Distribution Measurements.

Thioflavin T (ThT) assay is extensively used for studying fibrillation kinetics in vitro. However, the differences in the time course of ThT fluorescence intensity and lifetime and other physical parameters of the system, such as particle size distribution, raise questions about the correct interpretation of the aggregation kinetics. In this work, we focused on the investigation of the mechanisms, which underlay the difference in sensitivity of ThT fluorescence intensity and lifetime to the formation of protein aggregates during fibrillation by the example of insulin and during binding to globular proteins. The assessment of aggregate sizes and heterogeneity was performed using dynamic light scattering (DLS) and nanoparticle tracking analysis (NTA). Using the sub-nanosecond resolution measurements, it was shown that the ThT lifetime is sensitive to the appearance of as much as a few percent of ThT bound to the high-affinity sites that occur simultaneously with an abrupt increase of the average particle size, particles concentration, and size heterogeneity. The discrepancy between ThT fluorescence intensity and a lifetime can be explained as the consequence of a ThT molecule fraction with ultrafast decay and weak fluorescence. These ThT molecules can only be detected using time-resolved fluorescence measurements in the sub-picosecond time domain. The presence of a bound ThT subpopulation with similar photophysical properties was also demonstrated for globular proteins that were attributed to non-specifically bound ThT molecules with a non-rigid microenvironment.

IVR Dynamics of Vibrational Levels of the ν1 Mode in (CF3)2C═C═O Molecules Excited by Resonant IR Femtosecond Radiation.

The intramolecular dynamics of vibrational levels (up to v = 5) of the ν1 mode in the (CF3)2CCO molecule that is induced by a multiphoton selective excitation of this mode by resonant femtosecond IR radiation has been studied. The times of intramolecular vibrational energy redistribution (IVR) from each vibrational level to remaining molecular modes have been determined. In accordance with theoretical predictions, a decrease in the IVR time with increasing quantum number v has been observed for the first time. A sharp decrease in the IVR time (down to 1.5 ps) at a wavelength of 2129 cm-1, corresponding to the v = 3 → v = 4 vibrational transition, is revealed. It has been shown that, with a negative chirp of a femtosecond radiation pulse, the population of high-lying vibrational levels of the ν1 mode increases significantly.

Short-lived intermediates in photochemistry of an OsCl62- complex in aqueous solutions.

Two mechanisms of OsIVCl62- photolysis were studied by means of quantum chemical calculations in gas and aqueous phases. The difference between these mechanisms is in the nature of the possible Os(iv) key intermediates (KI). According to calculations, the intermediate is an OsIVCl5- complex of square pyramidal coordination geometry. The calculations do not give an opportunity to make an unambiguous choice between the triplet and quintet multiplicities of OsIVCl5-. The calculated CASSCF/IMCP-SR1 transition energies for 5OsIVCl5- are lower than for 3OsIVCl5-, while the calculated XMC-QDPT2/SBKJC spectra for the triplet state are in better agreement with the experimental absorption spectrum of the KI than for the quintet state.

Primary photochemical processes for Pt(iv) diazido complexes prospective in photodynamic therapy of tumors.

Diazide diamino complexes of Pt(iv) are considered as prospective prodrugs in oxygen-free photodynamic therapy (PDT). Primary photophysical and photochemical processes for cis,trans,cis-[Pt(N3)2(OH)2(NH3)2] and trans,trans,trans-[Pt(N3)2(OH)2(NH3)2] complexes were studied by means of stationary photolysis, nanosecond laser flash photolysis and ultrafast kinetic spectroscopy. The process of photolysis is multistage. The first stage is the photosubstitution of an azide ligand to a water molecule. This process was shown to be a chain reaction involving redox stages. Pt(iv) and Pt(iii) intermediates responsible for the chain propagation were recorded using ultrafast kinetic spectroscopy and nanosecond laser flash photolysis. The mechanism of photosubstitution is proposed.

Primary photophysical and photochemical processes for hexachloroosmate(iv) in aqueous solution.

The photoaquation of the OsIVCl62- complex was studied by means of stationary photolysis, nanosecond laser flash photolysis and ultrafast kinetic spectroscopy. The OsIVCl5(OH)2- complex was found to be the only reaction product. The quantum yield of photoaquation is rather low and wavelength-dependent. No impact of redox processes on photoaquation was revealed. The total characteristic lifetime of the process is about 80 ps. Three intermediates were recorded in the femto- and picosecond time domains and assigned to different Os(iv) species. The nature of intermediates and possible mechanisms of photoaquation are discussed.

Ultrafast dissociation dynamics of [Fe(CO)5](n) clusters induced by femtosecond IR radiation.

Using the femtosecond time-resolved infrared pump-visible probe technique, we have measured for the first time the ultrafast dissociation dynamics of [Fe(CO)5]n clusters induced by IR resonant excitation of C≡O vibrational modes in the 5-µm region. Free Fe(CO)5 molecules formed as a result of the cluster dissociation have been ionized by the femtosecond laser radiation at λ = 400 nm and have been detected with a time-of-flight mass-spectrometer. The temporal dependence of the yield of free molecules has been measured under different conditions of the IR laser excitation. We have proposed a model that describes well experimental results and makes it possible to calculate the temporal profile of the cluster temperature in terms of the concept of the evaporative ensemble. The rates of the intramolecular and intracluster vibrational relaxation in [Fe(CO)5]n clusters have been estimated.

Ultrafast photophysical processes for Fe(III)-carboxylates.

Photochemical reactions with the participation of iron(iii) carboxylates are important for environmental photochemistry and have a great potential of application in water purification (advanced oxidation processes, photo-Fenton and Fenton-like processes). In spite of this, information about excited states and primary intermediates in the photochemistry of Fe(iii) complexes with carboxylic acids is scarce. This mini-review presents and discusses the results of several recent publications in the field of ultrafast spectroscopy of natural Fe(iii) carboxylates.

Intramolecular vibrational dynamics in free polyatomic molecules with C═O chromophore bond excited by resonant femtosecond IR laser radiation.

In nine polyatomic molecules, we have studied the intramolecular redistribution of vibrational energy from chromophore C═O group excited by a resonant femtosecond IR laser radiation at a wavelength of ∼5 µm. All experiments have been performed in the gas phase using the IR-IR pump-probe technique in combination with the spectral analysis of the probe radiation. For molecules with one C═O end group, characteristic times of intramolecular vibrational redistribution (IVR) lie in the range between 2.4 and 20 ps and correlate with the density of four-frequency Fermi resonances. The IVR times in metal carbonyl molecules are anomalously long, being ∼1.0 ns for Fe(CO)5 and ∼1.5 ns for Cr(CO)6. In the CH3(C═O)OC2H5 and H2CCH(C═O)OC2H5 molecules, it has been observed that there are two characteristic IVR times, which differ by an order of magnitude from each other; this was interpreted in terms of the developed model of "accumulating states". For the ICF2COF molecule, it has been revealed that the IVR time decreases with increasing level of the vibrational excitation of the C═O bond of the molecule.