A New Approach to Increasing the Resolution of a Mass Spectrometer with Wedge-Shaped Reflectors

The paper describes the investigation of the ion-optical properties of a laser TOF mass spectrometer including two successively positioned wedge-shaped ion mirrors. Some specific properties of the configuration of ion trajectories near their reflection in the second ion reflector are found. The dependence of aberrations on ion energy acquired toothed shape for the resolution of the analyzer higher than 3000–5000. The approximation of the dependence gave a 15^th degree polynomial. The calculation of polynomial coefficients showed a great contribution to the duration of ion packets for aberrations of higher order. The discovered features allowed us to suggest a way of the local correction of nearby trajectories in the total ion flux. By correcting the local motion of individual groups of ions, we could reduce temporary aberration to 1–1.6 ns, depending on ion energy. For the time of ion flight ~35 μs, such duration limits the resolution of the analyzer by a value not less than 10000. The real length of ion drift path was about 30 cm. The total overall sizes of the ionoptical system were ~24 × 19 × 5 cm.     

Determination of explosive vapor concentrations with remote sampling in the control of objects

A procedure is proposed for the determination of the vapor concentration of 2,4,6-trinitrotoluene (TNT) in air at a level of 10^–16 g/cm³ in the control of objects for the presence of TNT. The procedure includes preconcentration of TNT vapors and gas chromatographic determination with a limit of TNT detection at a level of 0.08 ± 0.02 pg in a sample. The procedure was applied to the control objects in cells of typical automatic luggage locker with sampling through sampling air ducts. A measure of sample losses as the breakthrough of vapors through sampling air ducts and gas dynamic conditions for the reduction of vapor losses as the ratio of diffusion coefficient to the air duct flow rate were proposed. The time constant of the saturation of the sampling system with TNT vapors and the time constant of its cleaning were determined. It was shown that TNT vapors can be detected virtually satisfactorily near TNT-containing objects with sampling through long channels.     

Primary photophysical and photochemical processes for Pt(SCN)<Subscript>6</Subscript><Superscript>2–</Superscript> complex

Photosolvation of a Pt^IV hexathiocyanate complex Pt(SCN)₆ ^2– in water and ethanol was studied by steady-state photolysis, nanosecond laser flash photolysis, and ultrafast kinetic spectroscopy. Complexes Pt(SCN)₅(H₂O)^– and Pt(SCN)₅(C₂H₅OH)^– were found to be the only reaction products. The quantum yields of photosolvation are independent of the excitation wavelength, being equal to 0.25 and 0.5 for the solutions of the complex in water and ethanol, respectively. Photosolvation proceeds by the mechanism of heterolytic metal—ligand bond dissociation without involvement of redox processes. The characteristic time of formation of the end products for both solvents is about 10 ps. Three successive intermediates detected on the picosecond time scale were interpreted as Pt^IV complexes. The nature of the intermediates and possible mechanisms of photosolvation are discussed.     

Alkylation of phenol with olefins in the presence of catalysts based on mesoporous aromatic frameworks

Mesoporous polyaromatic frameworks (PAFs) based on tetraphenylmethane were obtained and modified with sulfonic acid groups. The compounds were characterized by solid-state ¹³C NMR and IR spectroscopy, low-temperature nitrogen adsorption-desorption, and transmission electron microscopy. The acidities of the PAF-1-SO₃H and PAF-2-SO₃H samples determined by titration were 3.99 mmol g^–1 and 0.91 mmol g^–1, respectively. The catalytic activity of PAF-SO₃H for alkylation of phenol with linear terminal olefins was investigated. The reaction products were isomeric monoalkylphenols (C-alkylates), and alkyl phenyl ethers (O-alkylates).     

The importance of glyceraldehyde radiolysis in chemical evolution

Studies in chemical evolution are intended to demonstrate how compounds of biological importance are generated from substances that could have been found in abiotic conditions on the primitive Earth or in extraterrestrial environments. In this context, the aim of the present work was to examine the behavior of dl-glyceraldehyde in both aqueous solution and solid samples under gamma irradiation. We irradiated dl-glyceraldehyde at different doses and temperatures with a gamma source; even at low doses and temperature (77 K), free radicals were detected. Among the products formed were ethylene glycol and glycolaldehyde. Some sugar-like compounds were also detected.

     

New two stages high order symmetric six-step method with vanished phase–lag and its first,second and third derivatives for the numerical solution of the Schrödinger equation

In the present paper, we obtain and analyze, for the first time in the literature, a new two-stages high order symmetric six-step method. The specific characteristics of the new proposed method are the highest possible algebraic order, the elimination of the phase–lag and its first, second and third derivatives. Additionally, for the new method we give the analysis of the method (both error and stability and interval of periodicity analysis) and the comparison of the effectiveness of the new developed method with the effectiveness of well known methods and very recently produced methods in the literature. The comparison is based on the numerical solution of the Schrödinger equation. The theoretical achievements and the numerical results show the effectiveness of the new developed method in comparison with other well known or recently developed numerical methods.     

An efficient and computational effective method for second order problems

An efficient and computational effective algorithm is introduced, for the first time in the literature, in the present paper. The main properties of the scheme are: (1) the algorithm is a two-step scheme, (2) the algorithm is symmetric one, (3) it is a hight algebraic order scheme (i.e of eight algebraic order), (4) it is a three-stages algorithm, (5) the first layer of the new method is based on an approximation to the point \(x_{n-1}\), (6) the scheme has vanished phase-lag and its first, second and third derivatives, (7) the new proposed algorithm has an interval of periodicity equal to \(\left( 0, 9.8 \right) \). For the present new scheme we study: (1) its construction, (2) its error analysis (3) its stability analysis. Finally, the investigation of the effectiveness of the new algorithm leads to its application to systems of differential equations arising from the Schrödinger equation.     

On the effectiveness of exponential type orbitals with hyperbolic cosine functions in atomic calculations

Unconventional basis functions, constructed from exponential type orbitals (ETOs) with hyperbolic cosine functions, are applied to Roothaan-Hartree-Fock calculations of atoms within the minimal basis sets framework. The most popular ETOs, Slater type orbitals, B functions and \(\psi ^{(\alpha ^*)}\) functions with \(\alpha ^*=2\), and two types of hyperbolic cosine functions, \(\cosh (\beta r)\) and \(\cosh (\beta r+\gamma )\), are used in this work. The performance of the present basis functions is investigated and compared to the conventional double-zeta Slater-type basis set and numerical Hartree-Fock results. The improvement in the atomic energies clearly demonstrates how the accuracy increases when we move from ETO to ETO with hyperbolic cosine basis functions. The resulting improved minimal basis sets can also be useful in molecular calculations.     

Study of oriented polyethylene structures using a Raman longwave acoustic mode

This paper concerns the basics of using longwave (low-frequency) Raman spectroscopy in the region of a longitudinal acoustic mode for the study of structural features of polymers. Using ultrahighmolecular- weight polyethylene (UHMW PE)-based reactor powders, gels, and oriented fibers obtained by the gel technology, the length distribution of straight-chain segments and its relation to the morphology of the sample were analyzed. An important role of the low-frequency Raman spectroscopy in creating domestic gel technology for preparing ultrahigh-strength threads from polyethylene was demonstrated.     

Application of numerical schemes with singling out the boundary layer for the computation of turbulent flows using eddy-resolving approaches on unstructured grids

The use of eddy-resolving approaches to solving problems on arbitrary unstructured grids is investigated. The applications of such approaches requires the use of low dissipation numerical schemes, which can lead to numerical oscillations of the solution on unstructured grids. Numerical oscillations typically occur in domains with large gradients of velocities, in particular, in the near-wall layer. It is proposed to single out the boundary layer and use a numerical scheme with increased numerical dissipation in it. The algorithm for singling out the boundary layer uses a switching function to change the parameters of the numerical scheme. This algorithm is formulated based on the BCD scheme from the family NVD. Its validity and advantages are investigated using the zonal RANS–LES approach for solving some problems of turbulent flow of incompressible fluids.