Emission excitation spectra and photochemistry of the 3820 Å band system of propynal

The fluorescence and phosphorescence excitation spectra of propynal at 0.60 torr with and without an added 100 torr He were measured up to an excess vibrational energy of 6000 cm^-1 above the zero-point level of S₁(¹A″). Over the same energy range, the relative quantum yield of the photoproduct CO was determined as a function of the excess energy. From these data it is suggested that the singlet S₁ is the photochemically active state, and that the collision-induced intersystem crossing process governs the photochemistry.     

Low temperature vibrational relaxation of carbon monoxide by light mass species

The rates of deactivation of CO(v=1) by ⁴He and by ³He have been measured between 300 K and 80 K using a pulsed laser fluorescence technique. The results show the usual strong deviation from Landau—Teller behaviour and a marked isotope effect. Comparison is made with theoretical predictions including a one-dimensional treatment which takes account of attractive forces. The present results are compared also with earlier work on the deactivation of CO by H₂, HD and D₂. It has been found that at and below 300 K D₂ is less efficient than ⁴He in the (VT) deactivation of CO (v=1) and HD is anomalously efficient. The latter effect is attributed to the involvement of rotational transitions.     

Damage in Y-Ba-Cu-O films produced by4He ions

The question of destructibility of an ion beam technique applied to the analysis of high temperature superconductors is discussed, namely the influence of the often used analyzing⁴He ion beam on a monocrystalline YBa₂Cu₃O₇ film. The rate of irradiation defect production is measured for 1 and 3.07 MeV⁴He⁺ irradiation and compared with a Monte Carlo simulation. It is shown that the usual depth profiling by⁴He ion beams does not change the measured element profiles, but is destructive from the view point of the superconducting properties of a sample, due to the great number of defects produced. Using a large solid angle detector one can minimize the analyzing dose to avoid the destruction of superconducting properties.     

Laser photolysis studies of hydrazine vapor: 193 and 222-nm H-atom primary quantum yields at 296 K,and the kinetics of H + N2H4 reaction over the temperature range 222–657 K

The primary quantum yield of H-atom production in the pulsed-laser photolysis of hydrazine vapor, N₂H₄ + hν → H + N₂H₃, was measured to be (1.01 ± 0.12) at 193 nm relative to HBr photolysis, and (1.06 ± 0.16) at 222 nm relative to 248-nm N₂H₄ photolysis, in excess He buffer gas at 296 K. The H-atoms were directly monitored in the photolysis by cw-resonance fluorescence detection of H(²S) at 121.6 nm. The high H-atom yield observed in the photolysis is consistent with the continuous ultraviolet absorption spectrum of N₂H₄ involving unit dissociation of the diamine from repulsive excited singlet state(s). The laser photodissociation of N₂H₄ was thus used as a ‘clean’ source of H-atoms in excess N₂H₄ and He buffer gas to study the gas-phase reaction, H + N₂H₄ → products; (k₁), in a thermostated photolysis reactor made of quartz or Pyrex. The pseudo-first-order temporal profiles of [H] decay immediately after photolysis were determined for a range of different hydrazine concentrations employed in the experiments to calculate the absolute second-order reaction rate coefficient, k₁. The Arrhenius expression was determined to be k₁ = (11.7 ± 0.7) × 10^?12 exp[?(1260 ± 20)/T] cm³ molec^?1 s^?1 in the temperature range 222–657 K. The rate coefficient at room temperature was, within experimental errors, independent of the He buffer gas pressure in the range 24.5–603 torr. The above temperature dependence of k₁ is in excellent agreement to that we determine in our discharge flow-tube apparatus in the temperature range 372–252 K and in 9.5 torr of He pressure. The Arrhenius parameters we report are consistent with a metathesis reaction mechanism involving the abstraction of hydrogen from N₂H₄ by the H-atom. © 1995 John Wiley & Sons, Inc.     

Detection of tritium and alpha decaying radionuclides in L/ILW by measurements of helium isotopes

As decay products, helium isotopes can clearly indicate the presence of tritium and alpha decaying isotopes in a closed system. This study presents the helium and neon measurements and their interpretation of long-term headspace gas investigations in L/ILW waste drums from Paks Nuclear Power Plant and closed vaults of the Radioactive Waste Treatment and Disposal Facility, Püspökszilágy, Hungary. Development of special sampling methods and preparation lines as well as isotope-analytical measurements of the headspace gas samples were done in the Hertelendi Laboratory of Environmental Studies in the ATOMKI. In the gas samples helium isotopes as well as neon isotopes have been determined mass spectrometrically. While neon content can be of atmospheric origin only, helium can be produced either by alpha decay (⁴He) or decay of tritium (³He). ³H/⁴He and He/Ne ratios have been used to determine the different origin of the helium isotopes. Helium isotope ratios always represented ³He enrichment in the headspace gases produced by the decay of the tritium in the waste. Using the recent ³He concentration in headspace gas the total amount of ³H restored in L/ILW vaults was estimated. The investigated seven different vaults were closed between 1979 and 1995 when they had been full with L/ILW. The calculated tritium activities based on the He measurements showed good agreement with the documented isotope inventory of the vaults. Typical tritium activity concentrations were between 0.1 and 10 Bq/L gas in the drums and between 10 and 1000 Bq/L gas in the vaults. Additionally, one drum showed a higher He/Ne ratio compared to air, which clearly indicates ⁴He excess, thus the presence an alpha source in the waste.     

Neutron energy spectra of 252Cf, Am-Be source and of the D(d,n)3He reaction

The neutron energy spectrum of the following sources were measured using a fast neutron spectrometer with the NE-213 liquid scintillator: ²⁵²Cf, Am-Be and D(d,n)³He reaction from a 3 MeV Pelletron accelerator in Tokyo Institute of Technology. The measured proton recoil pulse height data of ²⁵²Cf, Am-Be and D(d,n)³He were unfolded using the mathematical program to obtain the neutron energy spectrum. The ²⁵²Cf and Am-Be neutron energy spectra were measured and the results obtained showed a good agreement with the spectra usually published in the literature. The neutron energy spectrum from D(d,n)³He was measured and the results obtained also showed a good agreement with the calculation by time of flight (TOF) methods.     

Surface potentials and A3He bound state on liquid 4He

Continuous surface potentials are calculated for both ⁴He and ³He at T = OK. Comparison of the derived heats of vaporization with the experimental ones shows good agreement. The energy of a ³He bound state on liquid ⁴He is also calculated: our results, —5.85K, is to be compared with the experimental one, —5.20K.     

3He Impurities in Nearly Frictionless Transport of Solid 4He at Low Temperatures

Glassy matter, when subjected to high shear rates exhibit shear thinning, that is, the viscosity diminishes with increasing shear rate. One possible outcome for the almost vanishing viscosity is nearly frictionless transport, which is possible in solid ⁴He due to the presence of minute concentrations of ³He. The glassy state of solid ⁴He is also relevant to the possible onset of superuidity in solid ⁴He. By treating the solid ⁴He locally as an amorphous matter and using the transition‐rate dependent model together with the specific activation energy, we observe a series of sudden changes of the shearing stresses (which directly relates to the resistance) at corresponding onset temperatures of supersolid ⁴He (ranging from 175 to 1200 mK) for different activation volumes of ³He. Even at higher concentrations of ³He than previous reported (around 1700 ppm), the supersolidity of ⁴He still occurs.     

Flash photolysis study of the NO-catalyzed recombination of bromine atoms

The recombination of bromine atoms at room temperature has been studied by flash photolysis in the range of 1–100 atm of the inert diluent He, leading to a value for the third-order rate constant of (1.5 ± 0.2) × 10¹⁵ cm⁶/mol².sec. In the presence of NO the recombination is considerably accelerated. The falloff curve of the recombination Br + NO (+He) → BrNO (+He) was also measured resulting in a value for the limiting low-pressure rate constant of (3.4 ± 1.3) × 10¹⁵ cm⁶/mol².sec. In experiments with excess NO, rate constants of (2.2 ± 1) × 10¹⁴ cm³/mol·sec for the reaction Br + BrNO → Br₂ + NO, and (6.1 ± 0.4) × 10⁹ cm⁶/mol².sec for the reaction Br₂ + 2NO → 2BrNO were obtained.     

Trace determination of zirconium using charged particle activation

Reaction yields on thick zirconium targets with proton, deuteron,³He and⁴He activation have been measured and compared. The most favorable reaction combining high sensitivity and selectivity was found to be Zr(p, xn)⁹⁰Nb. The absolute cross-section for this excitation function has been measured for proton energies up to 20 MeV. Analytical applications are illustrated with nondestructive zirconium analyses in glass. Yields from the thick target experiments indicate that the detection limit for this zirconium analysis method is ～1 ppb.     

Excess volume of mixing of some electron-donating hydrocarbons with an electron-accepting liquid 1,2,4-trichlorobenzene

The excess volume of mixing of some electron-donating aromatic hydrocarbons like benzene, toluene,p-xylene, and mesitylene with an electronaccepting liquid 1,2,4-trichlorobenzene have been measured at 30°C. The results indicate that the interaction between the components increases as the electron-donating power of the hydrocarbons increases. The V _m ^e values are related to the ionization potentials of the hydrocarbons.     

Extraterrestrial3 He in marine polymetallic nodules: A potential method for measuring growth rate of nodules

The comparative measurements of helium isotope compositions between marine polymetallic nodules and their surrounding sediments, their magnetic fractions and bulk from C-C Zone of the East Pacific Basin are reported. The⁴He content and³He/⁴He ratio of polymetallic nodules and their surrounding sediments are extremely high; the³He,⁴ He concentrations and most³He/⁴He ratios of magnetic fractions in nodules and sediments are apparently higher than those in bulk. The helium isotope data points of nodules and sediments are all distributed along or closely to the mixing curve of the interplanetary dust particles (IDPs) and the terrigenous sediments in the chart of³He-³He/⁴He. In the same sampling site, the³He/⁴He ratios of nodules and their surrounding sediments are very similar, and the changes of both ratios are synchronous. It shows that the high³He/⁴He ratios in nodules and sediments may all result from IDPs. So, if the flux of extraterrestrial³He into the nodules and sediments is constant, the growth rate of polymetallic nodules and the sedimentation rate of sediments can be independently calculated according to the concentra-tion of extraterrestrial³He in nodules and sediments.

     

Determination of tritium in Li–Pb alloy irradiated by thermal neutrons with quantitatively analyzing the byproduct 4He

The mass of the tritium produced in ⁶Li(n,α)T reaction was obtained by quantitatively analyzing the byproduct ⁴He with mass spectrometer. The self-expending seal method was employed to quantitatively prepare the Li–Pb alloy targets in room temperature. They were irradiated for 2 h in two rabbit irradiation channels in Xi’an pulsed reactor and measured after cooling 15 days. A sample purifying unit was set up to get rid of the hydrogen isotopes to remarkably reduce the interference to helium isotopes when measuring. And the sample disposal platform including purifying unit was testified with simulative gas and nature atmosphere. The targets were melted at 700 °C to release most of the ⁴He atoms which were measured by adding dilution gas ³He. And it was testified that ⁴He had released completely by repetitiously melting the targets. This approach had solved the problem that the tritium couldn’t be accurately determined by directly analyzing it because of non-complete releasing from lithium alloy.     

Simultaneous electron capture and target ion excitation in collisions of C4+ and N5+ on He

Cross sections for simultaneous electron capture and target ion excitation have been measured for impact of slow He-like C⁴⁺ and N⁵⁺ ions on He. The energy of the primary ion beams has been varied over more than two orders of magnitude: 0.05–7 keV/amu. The results are discussed on basis of a slightly modified version of the dynamic classical over-barrier model for multiple electron capture. The differences in the energy dependences of the experimental results of C⁴⁺ and N⁵⁺ — He can be explained qualitatively by assuming that for N⁵⁺ binding energy sharing between the two participating electrons is of importance, particularly at the lower impact energies.     

Electron impact ionization of CCl4 and SF6 embedded in superfluid helium droplets

Electron impact ionization of helium nano-droplets containing several 10⁴ He atoms and doped with CCl₄ or SF₆ molecules is studied with high-mass resolution. The mass spectra show significant clustering of CCl₄ molecules, less so for SF₆ under our experimental conditions. Positive ion efficiency curves as a function of electron energy indicate complete immersion of the molecules inside the helium droplets in both cases. For CCl₄ we observe the molecular parent cation CCl₄⁺ that preferentially is formed via Penning ionization upon collisions with He*. In contrast, no parent cation SF₆⁺ is seen for He droplets doped with SF₆. The fragmentation patterns for both molecules embedded in He are compared with gas phase studies. Ionization via electron transfer to He⁺ forms highly excited ions that cannot be stabilized by the surrounding He droplet. Besides the atomic fragments F⁺ and Cl⁺ several molecular fragment cations are observed with He atoms attached.     

Extraterrestrial<Superscript>3</Superscript> He in marine polymetallic nodules: A potential method for measuring growth rate of nodules

The comparative measurements of helium isotope compositions between marine polymetallic nodules and their surrounding sediments, their magnetic fractions and bulk from C-C Zone of the East Pacific Basin are reported. The⁴He content and³He/⁴He ratio of polymetallic nodules and their surrounding sediments are extremely high; the³He,⁴ He concentrations and most³He/⁴He ratios of magnetic fractions in nodules and sediments are apparently higher than those in bulk. The helium isotope data points of nodules and sediments are all distributed along or closely to the mixing curve of the interplanetary dust particles (IDPs) and the terrigenous sediments in the chart of³He-³He/⁴He. In the same sampling site, the³He/⁴He ratios of nodules and their surrounding sediments are very similar, and the changes of both ratios are synchronous. It shows that the high³He/⁴He ratios in nodules and sediments may all result from IDPs. So, if the flux of extraterrestrial³He into the nodules and sediments is constant, the growth rate of polymetallic nodules and the sedimentation rate of sediments can be independently calculated according to the concentra-tion of extraterrestrial³He in nodules and sediments.     

Molecular ramsauer-townsend effect in very low energy He-He scattering

It is shown that a Ramsauer-Townsend effect is possible in very low energy (≈ 2°K) collisions of ⁴He-⁴He - i.e., a deep minimum in the total elastic scattering cross section occurs at this collision energy. It is seen that no such minimum is possible for the other isotopic variants, ³He-³He and ³He-⁴He.     

Spatially resolved temperature measurements in a furnace atomization plasma excitation spectrometry source

Spatially resolved atomic emission intensities from helium, and molecular emission intensities from OH and N⁺₂ have been measured in a furnace atomization plasma excitation spectrometry (FAPES) source. He I emission at 388.86 nm was used to monitor the spatial structure of the plasma in the source while increasing the radio frequency (r.f.) power applied to its center electrode. At higher r.f. power the He I emission intensity increased significantly while its spatial structure remained relatively unchanged. The He I emission was found to be most intense adjacent to the center electrode. Some less intense emission was observed adjacent to the graphite cuvette wall and some very weak emission was seen throughout the volume of the source. These observations suggest that the FAPES source operates as an r.f. glow discharge.Emission intensities from the OH (0-0) rotational A ²Σ⁺ → X ²Π_i and N⁺₂ (0-0) rotational B ²Σ⁺_o → ²Σ⁼_g bands were used to monitor the effects of increasing the r.f. power applied to the center electrode of the source. From these measurements, rotational temperatures for these molecules were calculated. The intensity measurements showed that there is a significant thermal gradient in the source with OH rotational temperatures ranging between 680 and 1050 K and N⁺₂ rotational temperatures ranging between 580 and 1920 K with 60 W r.f. power applied to the center electrode. At higher r.f. powers there is an increase in rotational temperatures and an increase in the dissociation of molecular species in the FAPES source.Lead excitation temperatures were calculated using the line ratio method by measuring the emission of the Pb I 280.119 and 283.306 nm lines at different r.f. powers. The temperature was found to increase monotonically with r.f. power over the range of 35 to 75 W.     

The determination of trace oxygen in lead by helium-3 and helium-4 activation analysis

The determination of oxygen in lead by³He and⁴He activation analysis was studied. Both methods were applied to the same material containing 0.9 μg·g^?1 of oxygen. The¹⁸F formed from oxygen was separated from matrix activities by extraction of Po with N-benzoyl-N-fenylhydroxylamine, followed by distillation of fluorosilicic acid and precipitation of lead fluorochloride (⁴He activation) or by distillation followed by precipitation (³He activation). The yield of the separation, which amounted on the average to 68%, was determined via the¹⁹F(n,⁴He)¹⁶N reaction. The coefficients of variation were 21 and 45% for⁴He and³He activation analysis, respectively, thus indicating a less homogeneous distribution of the oxygen. Nuclear interferences of sodium and fluorine were shown to be negligible.     

The enthalpies and entropies of dilution of alkali halides and tetraalkylammonium halides in N-methylacetamide

The enthalpies of dilution of some alkali and tetraalkylammonium halides have been measured in N-methylacetamide at 35°C. The results approach the Debye-Hückel limiting law at low concentrations. Excess free energies and entropies were calculated from the present results and previous freezing point measurements. The excess enthalpies of the alkali halides in N-methylacetamide are in the same range as the excess enthalpies in water. The effect of changing anions is quite small in N-methylacetamide. The cation order is Li⁺?Na⁺>Cs⁺>K⁺. The excess enthalpies of the tetraalkylammonium halides in N-methylacetamide are very different from the excess enthalpies in water, confirming the conclusion that in water the large excess enthalpies are due to hydrophobic bonding and that in N-methylacetamide this effect is not present.