Supercontinuum saturation of a femtosecond laser filament in pressurized gases.

Filamentation of high-power femtosecond optical pulses in high-pressure gases has gained increasing academic and practical interest from the viewpoint of studying large-scale spectral and temporal transformations occurring with pulsed laser radiation and obtaining super-broadened spectra and extremely short (attosecond) wave packets. Experimentally and theoretically, for the first time to the best of our knowledge, we show that as a result of a 45 fs Ti:sapphire laser pulse filamentation in an optical cell filled with pressurized up to 50 bar nitrogen or argon, the pulse spectrum can reach maximally about eightfold broadening. This limiting pulse spectral width is reached at a gas pressure of about 20 bar and with further pressure increase exhibits saturation and even a slight decrease relative to the limiting value.

Observation of nonlinear fractal higher order topological insulator.

Higher-order topological insulators (HOTIs) are unique materials hosting topologically protected states, whose dimensionality is at least by 2 lower than that of the bulk. Topological states in such insulators may be strongly confined in their corners which leads to considerable enhancement of nonlinear processes involving such states. However, all nonlinear HOTIs demonstrated so far were built on periodic bulk lattice materials.

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.

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.

Observation of nonlinearity-controlled switching of topological edge states.

We report the experimental observation of the periodic switching of topological edge states between two dimerized fs-laser written waveguide arrays. Switching occurs due to the overlap of the modal fields of the edge states from topological forbidden gap, when they are simultaneously present in two arrays brought into close proximity. We found that the phenomenon occurs for both strongly and weakly localized edge states and that switching rate increases with decreasing spacing between the topological arrays.

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.

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.

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.

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

The intramolecular dynamics of vibrational levels (up to v = 5) of the ν mode in the (CF)CCO 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.

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

Two mechanisms of OsCl 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 OsCl complex of square pyramidal coordination geometry.

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(N)(OH)(NH)] and trans,trans,trans-[Pt(N)(OH)(NH)] complexes were studied by means of stationary photolysis, nanosecond laser flash photolysis and ultrafast kinetic spectroscopy. The process of photolysis is multistage.

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

The photoaquation of the OsCl complex was studied by means of stationary photolysis, nanosecond laser flash photolysis and ultrafast kinetic spectroscopy. The OsCl(OH) complex was found to be the only reaction product. The quantum yield of photoaquation is rather low and wavelength-dependent.

Phase-matched third-harmonic generation via doubly resonant optical surface modes in 1D photonic crystals.

Efficient nonlinear conversion requires that interacting optical waves maintain a consistent phase relationship when traveling in a medium despite its dispersion. Birefringent phase-matching, which is often used to compensate for the dispersion, is not applicable to optically isotropic nonlinear materials. Here, we present a one-dimensional photonic crystal structure that allows the propagation of optical surface waves, both at the fundamental and third-harmonic frequencies, as an efficient medium for phase-matched third-harmonic generation.

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.

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.