Metastable Conducting Crystalline Hydrogen at High Pressure

The quantum molecular dynamics method within the density functional theory has been used to calculate the equation of state, pair correlation function, and static electrical conductivity of solid hydrogen in the region of formation of a conducting phase. Hysteresis has been revealed on the density dependence of the pressure at a temperature of 100 K under compression and subsequent tension. The overlapping of branches of the isotherms of the molecular and nonmolecular phases of solid hydrogen corresponds to the region of existence of metastable states. The width of this region is 275 GPa. It has been shown that conducting crystalline nonmolecular hydrogen with P2₁/c symmetry can exist at extension to a pressure of 350 GPa.

     

Study of the Vibrational Spectrum of Hydrogen Molecules in an Aerogel

The pressure dependence of the absorption spectrum of hydrogen molecules inside pores of an aerogel has been found. Two components with linear and quadratic pressure dependences have been revealed. It has been assumed that the first component can be attributed to the absorption of an individual molecule near the surface of pores, whereas the second component is due to intermolecular interaction. A method has been proposed to estimate in the first approximation the size of pores from the absorption spectrum.

     

Some principles in choosing parameters of magnetic resonance tomographs

The problem of amplifying the signal that ensures the visualization of internal organs in the magnetic resonance tomograph due to the optimal selection of some of its parameters has been considered. The operating principle of the tomograph has been analyzed. The relation between the angle of the magnetic moment precession in hydrogen nuclei in an organism, the frequency of the ac magnetic field exciting this precession, and the constant magnetic field used has been determined using quantum-mechanical concepts. This relation makes it possible to determine the optimal parameters for tomograph operation.

     

Spectroscopic Studies of Proton Transfer Equilibria In Hydrogen Bonded Complexes

Abstract

Recent studies on proton transfer equilibria for many hydrogen bonded complexes are discussed. These studies employ various spectroscopic techniques as infrared, ultraviolet, ¹H NMR, ¹³C NMR, ¹⁵N NMR and nuclear quadrupole resonance (NQR) spectroscopy. Special attention has been paid to Fourier transform infrared (FTIR), and it forms the main focus of this review, in particular for the study of proton transfer equilibria in proton sponges hydrogen bonded complexes. The influence of proton transfer equilibria on the physical, chemical and biological properties of hydrogen bonded complexes is shown. Some applications of proton transfer equilibria are also discussed.

     

Production of Pure Hydrogen Peroxide Solutions in Water Activated by the Plasma of Electrodeless Microwave Discharge and Their Application to Control Plant Growth

A method for the production of pure solutions of hydrogen peroxide during water activation by the plasma of electrodeless microwave discharge has been developed. It is shown that activated water has a pronounced effect on agricultural plants, being a non-toxic and chemically pure regulator of biological activity. In particular, the treatment of seeds of agricultural plants with activated water solutions can improve their drought resistance.

     

Infrared Study of the Interaction of Tetramethylthiourea and Dimethylthioformamide with Phenol Derivatives

Abstract

The hydrogen bonded complexes between hydroxylic bonds and oxygen or nitrogen bases have been extensively studied by infrared spectrometry. However, meager experimental results are available for sulfur participation in hydrogen bond formation. There seems little doubt that in thioamides - hydroxylic complexes, the donor site for hydrogen bonding is sulfur, particularly in view of the blue shift of the n → π? transition of the thiocarbonyl group in proton donor solvents ¹. This paper reports on a study of the equilibrium constants (K) and on the frequency shifts of the 1 v _OH stretching vibration of hydrogen bonded complexes between tetramethylthiourea (TMTU) or dimethyltnioformamide (DMTF) and some phenol derivatives.     

On single-crystal neutron-diffraction in DACs: quantitative structure refinement of light elements on SNAP and TOPAZ

ABSTRACT

Quantitative single crystal neutron-diffraction in diamond anvil cells has so far been limited by the neutron flux available at the various neutron sources. As a result, highly precise measurements of the exact position of light elements have not been possible preventing, for example, structural studies of hydrogen and hydrogen bonds under pressure. Here we report experiments carried out on SNAP at the Spallation Neutron Source (ORNL, TN, USA) to explore the possibility and current limits of such studies. Furthermore, we benchmarked the obtained data quality with reference experiments carried out on TOPAZ, a dedicated single-crystal instrument.

We show that measuring single-crystal diffraction intensities on SNAP is possible to such a precision that we are able to resolve the hydrogen bonds in potassium dideuterium phosphate (DKDP) as well as in ice VI.     

A cryostat design for radiation damage experiments at low temperature

Abstract

A cryostat for electron irradiations at liquid hydrogen or helium temperatures is described. The cryostat uses two concentric liquid coolant containers, of which the inner reservoir is sealed and acts as a heat exchanger through ebullition and recondensation of the coolant gas. This allows irradiations with a power input from the beam of up to a few watts, and when the sample is thermally isolated allows it to be annealed up to room temperature.     

Stimulated Raman Scattering in Hydrogen Using Capilary Cell

Abstract

Stimulated Raman Scattering processes have been studied and intense Stokes and anti—Stokes laser lines have been observed in a capillary Raman cell filled with molecular hydrogen and pumped by the third harmonic of the Nd:YAG laser at wavelength ?D = 355 nm. Various parametric studies have been performed to establish an optimum condition for the best operation of the Raman laser. The observation of higher—order Stokes and anti—Stokes has been explained on the basis of four—wave mixing and/or cascade energy transfer processes.     

Hydrogen in the near-surface of crystalline silicon

Abstract

Real-time electric field drift experiments, in-situ capacitance-voltage profiling, deep-level transient spectroscopy and nuclear reaction analysis have been used to monitor hydrogen motion and passivation processes in silicon. Spontaneous hydrogen injection and very fast migration has been detected in the near-surface region of various Schottky barriers and p-n junctions. The effective hydrogen diffusivity is about 10^?8 cm²/s at 400 K in agreement with the estimated value obtained by extrapolation from the high-temperature diffusivity data. The results of real-time in-situ measurements clearly demonstrate that the fast diffusing protons are involved in the hydrogenation processes of both shallow and deep levels. The possible physicochemical mechanisms for the observed spontaneous hydrogen injection which results in unintentional hydrogenation of the subsurface of silicon, and probably other semiconductors, are discussed.     

The influence of hydrogen bonds upon diffusion of simple amines and binary mixtures of ammonia

Abstract

Self diffusion coefficients of monomethylamine and trimethylamine and intradiffusion coefficients of some model mixtures containing ammonia have been measured up to pressures of 200 MPa at temperatures between the melting pressure curve and 423 K by pulsed field gradient Spin Echo NMR. Compared to water and the lower alcohols the self diffusion coefficients of pure fluid ammonia shows no clear influence from hydrogen bonds in contrast to other thermodynamic properties. Therefore the methylated substance monomethylamine has been studied to see weather a more structured charge distribution on the molecular surface compared to ammonia is needed to hinder fast rearrangements of the hydrogen bonds. For comparison also trimethylamine has been studied where no hydrogen bonds can be formed. Additionally binary mixtures of ammonia with methanol, benzene, trimethylamine and acetonitrile have been studied to see effects of intermolecular interactions.     

Theoretical investigation of intramolecular π-type hydrogen bonding and internal rotation of 2-cyclopropen-1-ol, 2-cyclopropen-1-thiol and 2-cyclopropen-1-amine

ABSTRACT

Theoretical computations utilising both CCSD and MP2 methods and the cc-pVTZ basis set have been carried out to determine the structures of several conformations as well as the internal rotation potential energy functions for 2-cyclopropen-1-ol, 2-cyclopropen-1-thiol and 2-cyclopropen-1-amine. The energies and wavefunctions for these potential functions have also been computed. Each of these molecules has an energy minimum corresponding to a conformation with intramolecular π-type hydrogen bonding. The π bonding stabilisation is about 2.3?kcal/mole for the alcohol, 2.1?kcal/mole for the thiol, and about 2.5?kcal/mole for the amine. The results for the thiol demonstrate a rare example of intramolecular π-type hydrogen bonding. The calculated O–H, S–H, N–H, and C=C stretching frequencies have also been compared for the conformations with and without the π-type hydrogen bonding. The C=C stretching frequency is substantially lower in all cases for the hydrogen bonded conformers.     

Platinized Magnesium as Reducing Agent for Hydrogen Isotope Analysis

Abstract

Platinized magnesium has recently been proposed as a new reducing agent for the conversion of small quantities of water to hydrogen in a flame-sealed borosilicate glass tube at 400°C for isotopic analysis. The reagent, Mg-Pt, in contrast to zinc can be prepared in every laboratory by coating a magnesium granulate with a thin layer of platinum by reaction with H₂PtCl₆·6H₂O dissolved in acetone-ether mixture. Excellent reproducibility of the isotope ratios in hydrogen gas prepared from water samples has been obtained using 4 μl of water and 120 mg of the reagent.     

Time-Dependent Resonant Tunneling in a Double-Barrier Diode Structure

The elastic moduli of bilayer graphene nanomeshes, i.e., nanomeshes of bilayer graphene, where layers at the edges of “closed” holes are coupled to each other by a continuous network of sp²-hybridized atoms, have been calculated by ab initio methods. Structures with different configurations of holes in layers with AA, AB, and 30° stackings have been studied. It has been shown that the ultimate tensile strength of the nanomeshes under consideration is higher than that of graphene nanostructures and is comparable with the ultimate tensile strength of bilayer graphene and single-layer carbon nanotubes. A possible application of such strong nanomeshes as nanocontainers for hydrogen storage and other compressed gases has been also discussed.

     

Molecular dynamics simulations of compressed hydrogen

Abstract

Molecular dynamics simulations have been performed for highly compressed fluid hydrogen in the density and temperature regime of recent shock-compression experiments. Both density functional and tight-binding electronic structure techniques have been used to describe interatomic forces. Two tight-binding models of hydrogen have been developed with a single s-type orbital on each atom that reproduce properties of the dimer, of various crystalline structures, and of the fluid. The simulations indicate that the rapid rise in the electrical conductivity observed in the gas-gun experiments depends critically on the dissociated atoms (monomers). We find that the internal structure of warm, dense hydrogen has a pronounced time-dependent nature with the continual dissociation of molecules (dimers) and association of atoms (monomers). Finally, Hugoniots derived from the equations-of-state of these models do not exhibit the large compressions predicted by the recent laser experiments.     

Separation of Deuterium Isotope by Chemical Exchange between Hydrogen and Water Vapour

The separation factor of deuterium (α) for the exchange reaction between hydrogen and water vapour at 100 °C has been measured and was found to be equals to 2.52 and 2.50, depending on the used experimental technique.

An empirical equation relating the variation of the separation factor with temperature for such isotopic exchange reaction has been deduced. The values of α were calculated from 0–800 °C and indicated close agreement with those calculated from spectroscopic data.

Comparison of the deduced empirical equation with the general equation relating the separation factor with temperature for such reaction, allowed the calculation of the zero point energy, as well as the free energy as a function of temperature.     

Electrosynthesis of hydrogen peroxide via the reduction of oxygen assisted by power ultrasound

The electrosynthesis of hydrogen peroxide using the oxygen reduction reaction has been studied in the absence and presence of power ultrasound in a non-optimized sono-electrochemical flow reactor (20 cm cathodic compartment length with 6.5 cm inner diameter) with reticulated vitreous glassy carbon electrode (30 x 40 x 10 mm, 10 ppi, 7 cm(2)cm(-3)) as the cathode. The effect of several electrochemical operational variables (pH, volumetric flow, potential) and of the sono-electrochemical parameters (ultrasound amplitude and horn-to-electrode distance) on the cumulative concentration of hydrogen peroxide and current efficiency of the electrosynthesis process have been explored. The application of power ultrasound was found to increase both the cumulative concentration of hydrogen peroxide and the current efficiency. The application of ultrasound is therefore a promising approach to the increased efficiency of production of hydrogen peroxide by electrosynthesis, even in the solutions of lower pH (<12). The results demonstrate the feasibility of at-site-of-use green synthesis of hydrogen peroxide.     

Generation of a Low Flow Atmospheric Pressure Neon ICP

Abstract

A 27.12 MHz low flow (3 1/min), laminar flow, atmospheric pressure neon ICP has been generated. The forward power used is 500 W with a reflected power of less than 5 W. Using higher powers caused the plasma to either extinguish or form numerous filaments. The Hß line is used to determine an electron number density of 8 × 10¹³cm^?3. The N₂ ⁺(0, 0) and OH(0, 0) transitions did not readily emit. This fact, coupled with the low electron density and low input power, indicates a relatively cool plasma.     

Exchange of injected hydrogen isotopes between diffusing and trapped states in Al

Abstract

Exchange of hydrogen isotopes between diffusing and trapped populations was found with successive injections of 25 keV D₂ ⁺ and 100 or 140 keV H₂ ⁺ into Al surface by simultaneously detecting elastically recoilled hydrogen and deuterium using 2 MeV He⁺.

When backward diffusion of injected hydrogen toward surface was supposed to be impeded or by-passed by structural changes in the subsurface layer due to ion bombardment, effective replacement cross-section of about 1.4 × 10^?18 cm² was observed. Otherwise, namely when the hydrogen backward diffusion is supposed to be rather free, the effective cross section of about 7.8 × 10^?18 was observed.

Due to the difference in energy of the first and second injections, this phenomenon is different from that so called “isotopic exchange”, which occurs through collisional process.