On Landau and stochastic attractor pictures in the problem of transition to turbulence

Laminar-turbulent transition in circular Couette flow is discussed. Phenomenological equations are proposed describing the breakdown of azimuthal waves coherency. The correspondence is established between the flow turbulization and the stochastic attractor in the phase space of these equations. Evolution of attractor structure is investigated experimentally in terms of motion in some effective phase space. It is shown that during the transition to turbulence the increase in number of degrees of freedom is combined with the stochastic behaviour of rapid motion envelopes.     

Optical spin hall effect

A remarkable analogy is established between the well-known spin Hall effect and the polarization dependence of Rayleigh scattering of light in microcavities. This dependence results from the strong spin effect in elastic scattering of exciton polaritons: if the initial polariton state has a zero spin and is characterized by some linear polarization, the scattered polaritons become strongly spin polarized. The polarization in the scattered state can be positive or negative dependent on the orientation of the linear polarization of the initial state and on the direction of scattering. Very surprisingly, spin polarizations of the polaritons scattered clockwise and anticlockwise have different signs. The optical spin Hall effect is possible due to strong longitudinal-transverse splitting and finite lifetime of exciton polaritons in microcavities.     

Effects of Spiro-Cyclohexane Substitution of Nitroxyl Biradicals on Dynamic Nuclear Polarization

Spiro-substituted nitroxyl biradicals are widely used as reagents for dynamic nuclear polarization (DNP), which is especially important for biopolymer research. The main criterion for their applicability as polarizing agents is the value of the spin–spin exchange interaction parameter (J), which can vary considerably when different couplers are employed that link the radical moieties. This paper describes a study on biradicals, with a ferrocene-1,1′-diyl-substituted 1,3-diazetidine-2,4-diimine coupler, that have never been used before as DNP agents. We observed a substantial difference in the temperature dependence between Electron Paramagnetic Resonance (EPR) spectra of biradicals carrying either methyl or spirocyclohexane substituents and explain the difference using Density Functional Theory (DFT) calculation results. It was shown that the replacement of methyl groups by spirocycles near the N-O group leads to an increase in the contribution of conformers having J ≈ 0. The DNP gain observed for the biradicals with methyl substituents is three times higher than that for the spiro-substituted nitroxyl biradicals and is inversely proportional to the contribution of biradicals manifesting the negligible exchange interaction. The effects of nucleophiles and substituents in the nitroxide biradicals on the ring-opening reaction of 1,3-diazetidine and the influence of the ring opening on the exchange interaction were also investigated. It was found that in contrast to the methyl-substituted nitroxide biradical (where we observed the ring-opening reaction upon the addition of amines), the ring opening does not occur in the spiro-substituted biradical owing to a steric barrier created by the bulky cyclohexyl substituents.     

Effect of Laser-Induced Optical Breakdown on the Structure of Bsa Molecules in Aqueous Solutions: An Optical Study

The influence of laser radiation of a typical surgical laser on the physicochemical properties of the Bovine Serum Albumin (BSA) protein was studied. It was established that the physicochemical characteristics of optical breakdown weakly depend on the concentration of protein molecules. At the same time, the patterns observed for an aqueous solution of BSA irradiated with a laser for different time periods were extremely similar to the classical ones. It was established that after exposure to laser radiation, the optical density of protein solutions increases. At the same time, the intensity of BSA fluorescence due to aromatic amino acid residues decreases insignificantly after exposure to laser radiation. In this case, the position of the excitation and emission maximum does not change, and the shape of the fluorescence spot on 3D maps also does not change significantly. On the Raman spectrum after exposure to laser radiation, a significant decrease in 1570 cm⁻¹ was observed, which indicates the degradation of α-helices and, as a result, partial denaturation of BSA molecules. Partial denaturation did not significantly change the total area of protein molecules, since the refractive index of solutions did not change significantly. However, in BSA solutions, after exposure to laser radiation, the viscosity increased, and the pseudoplasticity of aqueous solutions decreased. In this case, there was no massive damage to the polypeptide chain; on the contrary, when exposed to optical breakdown, intense aggregation was observed, while aggregates with a size of 400 nm or more appeared in the solution. Thus, under the action of optical breakdown induced by laser radiation in a BSA solution, the processes of partial denaturation and aggregation prevail, aromatic amino acid residues are damaged to a lesser extent, and fragmentation of protein molecules is not observed.     

Polymer adsorption onto random planar surfaces: interplay of polymer and surface correlations

We study the adsorption of homogeneous or heterogeneous polymers onto heterogeneous planar surfaces with exponentially decaying site-site correlations, using a variational reference system approach. As a main result, we derive simple equations for the adsorption-desorption transition line. We show that it is preferable to have a small amount of strongly adsorbing sites or monomers rather than a greater amount of weakly adsorbing ones. The results are discussed with respect to their implications for the physics of molecular recognition.     

ML-Based Analysis of Particle Distributions in High-Intensity Laser Experiments: Role of Binning Strategy

When entering the phase of big data processing and statistical inferences in experimental physics, the efficient use of machine learning methods may require optimal data preprocessing methods and, in particular, optimal balance between details and noise. In experimental studies of strong-field quantum electrodynamics with intense lasers, this balance concerns data binning for the observed distributions of particles and photons. Here we analyze the aspect of binning with respect to different machine learning methods (Support Vector Machine (SVM), Gradient Boosting Trees (GBT), Fully-Connected Neural Network (FCNN), Convolutional Neural Network (CNN)) using numerical simulations that mimic expected properties of upcoming experiments. We see that binning can crucially affect the performance of SVM and GBT, and, to a less extent, FCNN and CNN. This can be interpreted as the latter methods being able to effectively learn the optimal binning, discarding unnecessary information. Nevertheless, given limited training sets, the results indicate that the efficiency can be increased by optimizing the binning scale along with other hyperparameters. We present specific measurements of accuracy that can be useful for planning of experiments in the specified research area.     

Structural rearrangements and magic numbers in reactions between pyridine-containing water clusters and ammonia

Molecular cluster ions H(+)(H(2)O)(n), H(+)(pyridine)(H(2)O)(n), H(+)(pyridine)(2)(H(2)O)(n), and H(+)(NH(3))(pyridine)(H(2)O)(n) (n = 16-27) and their reactions with ammonia have been studied experimentally using a quadrupole-time-of-flight mass spectrometer. Abundance spectra, evaporation spectra, and reaction branching ratios display magic numbers for H(+)(NH(3))(pyridine)(H(2)O)(n) and H(+)(NH(3))(pyridine)(2)(H(2)O)(n) at n = 18, 20, and 27. The reactions between H(+)(pyridine)(m)(H(2)O)(n) and ammonia all seem to involve intracluster proton transfer to ammonia, thus giving clusters of high stability as evident from the loss of several water molecules from the reacting cluster. The pattern of the observed magic numbers suggest that H(+)(NH(3))(pyridine)(H(2)O)(n) have structures consisting of a NH(4)(+)(H(2)O)(n) core with the pyridine molecule hydrogen-bonded to the surface of the core. This is consistent with the results of high-level ab initio calculations of small protonated pyridine/ammonia/water clusters.     

Molecular Structure,Thermodynamic and Spectral Characteristics of Metal-Free and Nickel Complex of Tetrakis(1,2,5-thiadiazolo)porphyrazine

The Knudsen effusion method with mass spectrometric control of the vapor composition was used to study the possibility of a congruent transition to the gas phase and to estimate the enthalpy of sublimation of metal-free tetrakis(1,2,5-thiadiazolo)porphyrazine and its nickel complex (H₂TTDPz and NiTTDPz, respectively). The geometrical and electronic structure of H₂TTDPz and NiTTDPz in ground and low-lying excited electronic states were determined by DFT calculations. The electronic structure of NiTTDPz was studied by the complete active space (CASSCF) method, following accounting dynamic correlation by multiconfigurational quasi-degenerate second-order perturbation theory (MCQDPT2). A geometrical structure of D_2h and D_4h symmetry was obtained for H₂TTDPz and NiTTDPz, respectively. According to data obtained by the MCQDPT2 method, the nickel complex possesses the ground state ¹A_1g, and the wave function of the ground state has the form of a single determinant. Electronic absorption and vibrational (IR and resonance Raman) spectra of H₂TTDPz and NiTTDPz were studied experimentally and simulated theoretically.