Nuclear weak interaction rates during stellar evolution and collapse

Nuclear weak interaction rates, including electron and positron emission rates, and continuum electron and positron capture rates , as well as the associated v and –/v energy loss rates are calculated on a detailed grid of temperature and density for the free nucleons and 226 nuclei with masses between A = 21 and 60. Gamow-Teller and Fermi discrete-state transition matrix element systematics and the Gamow-Teller T^< →/← T^> resonance transitions are discussed in depth and are implemented in the stellar rate calculations. Results of the calculations are presented on an abbreviated grid of temperature and density and comparison is made to terrestrial weak transition rates where possible. Neutron shell blocking of allowed electron capture on heavy nuclei during stellar core collapse is discussed along with several unblocking mechanisms operative at high temperature and density. The results of one-zone collapse calculations are presented which suggest that the effect of neutron shell blocking is to produce a larger core lepton fraction at neutrino trapping which leads to a larger inner-core mass and hence a stronger post-bounce shock.

I. Electron spin relaxation studies of manganese(II) complexes in acetonitrile. II. Nuclear spin relaxation studies of bromine in tetrabromomanganese(II) in acetonitrile

Magnetic resonance techniques have given us a powerful means for investigating dynamical processes in gases, liquids and solids. Dynamical effects manifest themselves in both resonance line shifts and linewidths, and, accordingly, require detailed analyses to extract desired information. The success of a magnetic resonance experiment depends critically on relaxation mechanisms to maintain thermal equilibrium between spin states. Consequently, there must be an interaction between the excited spin states and their immediate molecular environment which promote changes in spin orientation while excess magnetic energy is coupled into other degrees of freedom by non-radiative processes. This is well known as spin-lattice relaxation. Certain dynamical processes cause fluctuations in the spin state energy levels leading to spin-spin relaxation and, here again, the environment at the molecular level plays a significant role in the magnitude of interaction. Relatively few electron spin relaxation studies of solutions have been conducted and the present work is addressed toward the extension of our knowledge in this area and the retrieval of dynamical information from line shape analyses on a time scale comparable to diffusion controlled phenomena.

Specifically, the electron spin relaxation of three Mn⁺²3d⁵ complexes, Mn(CH₃CN)₆⁺², MnCl₄^-2 in acetonitrile has been studied in considerable detail. The effective spin Hamiltonian constants were carefully evaluated under a wide range of experimental conditions. Resonance widths of these Mn⁺² complexes were studied in the presence of various excess ligand ions and as a function of concentration, viscosity, temperature and frequency (X-band, ~9.5 Ԍ Hz and K-band, ~35 Ԍ Hz).

A number of interesting conclusions were drawn from these studies. For the Et₄NCl-₄^-2 system several relaxation mechanisms leading to resonance broadening were observed. One source appears to arise through spin-orbit interactions caused by modulation of the ligand field resulting from transient distortions of the complex imparted by solvent fluctuations in the immediate surroundings of the paramagnetic ion. An additional spin relaxation was assigned to the formation of ion pairs [Et₄N⁺…MnCl₄^-2] and it was possible to estimate the dissociation constant for this specie in acetonitrile.

The Bu₄NBr-MnBr₄^-2 study was considerably more interesting. As in the former case, solvent fluctuations and ion-pairing of the paramagnetic complex [Bu₄N⁺…MnBr₄^-2] provide significant relaxation for the electronic spin system. Most interesting, without doubt, is the onset of a new relaxation mechanism leading to resonance broadening which is best interpreted as chemical exchange. Thus, assuming that resonance widths were simply governed by electron spin state lifetimes, we were able to extract dynamical information from an interaction in which the initial and final states are the same

MnBr₄^-2 + Br^- = MnBr₄^-2 + Br^-.

The bimolecular rate constants were obtained at six different temperatures and their magnitudes suggested that the exchange is probably diffusion controlled with essentially a zero energy of activation. The most important source of spin relaxation in this system stems directly from dipolar interactions between the manganese 3d⁵ electrons. Moreover, the dipolar broadening is strongly frequency dependent indicating a deviation between the transverse and longitudinal relaxation times. We are led to the conclusion that the 3d⁵ spin states of ion-paired MnBr₄^-2 are significantly correlated so that dynamical processes are also entering the picture. It was possible to estimate the correlation time, ^Td, characterizing this dynamical process.

In Part II we study nuclear magnetic relaxation of bromine ions in the MnBr4-2-Bu4NBr-acetonitrile system. Essentially we monitor the 79Br and 81Br linewidths in response to the [MnBr4-2]/[Br-] ratio with the express purpose of supporting our contention that exchange is occurring between "free" bromine ions in the solvent and bromine in the first coordination sphere of the paramagnetic anion. The complexity of the system elicited a two-part study: (1) the linewidth behavior of Bu4NBr in anhydrous CH3CN in the absence of MnBr4-2 and (2) in the presence of MnBr4-2. It was concluded in study (1) that dynamical association, Bu4NBr k1= Bu4N+ + Br-, was modulating field-gradient interactions at frequencies high enough to provide an estimation of the unimolecular rate constant, k1. A comparison of the two isotopic bromine linewidth-mole fraction results led to the conclusion that quadrupole interactions provided the dominant relaxation mechanism. In study (2) the "residual" bromine linewidths for both 79Br and 81Br are clearly controlled by quadrupole interactions which appear to be modulated by very rapid dynamical processes other than molecular reorientation. We conclude that the "residual" linewidth has its origin in chemical exchange and that bromine nuclei exchange rapidly between a "free" solvated ion and the paramagnetic complex, MnBr4-2.

Applications of nuclear magnetic resonance spectroscopy to the study of medium-sized rings. I. Conformational properties of cycloheptane. II. Conformational properties of cycloöctane

Conformational equilibrium in medium-sized rings has been investigated by the temperature variation of the fluorine-19 n.m.r. spectra of 1, 1-difluorocycloalkanes and various substituted derivatives of them. Inversion has been found to be fast on the n.m.r. time scale at -180˚ for 1, 1-difluorocycloheptane, but slow for 1, 1-difluoro-4, 4-dimethylcycloheptane at -150˚. At low temperature, the latter compound affords a single AB pattern with a chemical-shift difference of 841 cps. which has been interpreted in terms of the twist-chair conformation with the methyl groups on the axis position and the fluorine atoms in the 4-position. At room temperature, the n.m.r. spectrum of 1, 1-difluoro-4-t-butylcycloheptane affords an AB pattern with a chemical-shift difference of 185 cps. The presence of distinct trans and gauche couplings from the adjacent hydrogens has been interpreted to suggest the existence of a single predominant form, the twist chair with the fluorine atoms on the axis position.

Investigation of 1, 1-difluorocycloöctane and 1, 1, 4, 4-tetrafluorocycloöctane has led to the detection of two kinetic processes both having activation energies of 8-10 kcal./mole but quite different A values. In light of these results eleven different conformations of cycloöctane along with a detailed description of the ways in which they may be interconverted are discussed. An interpretation involving the twist-boat conformation rapidly equilibrating through the saddle and the parallel-boat forms at room temperature is compatible with the results.

Polaron hopping in olivine phosphates studied by nuclear resonant scattering

Valence fluctuations of Fe²⁺ and Fe³⁺ were studied in a solid solution of Li_xFePO₄ by nuclear resonant forward scattering of synchrotron x rays while the sample was heated in a diamond-anvil pressure cell. The spectra acquired at different temperatures and pressures were analyzed for the frequencies of valence changes using the Blume-Tjon model of a system with a fluctuating Hamil- tonian. These frequencies were analyzed to obtain activation energies and an activation volume for polaron hopping. There was a large suppression of hopping frequency with pressure, giving an anomalously large activation volume. This large, positive value is typical of ion diffusion, which indicates correlated motions of polarons, and Li⁺ ions that alter the dynamics of both.

In a parallel study of Na_xFePO₄, the interplay between sodium ordering and electron mobility was investigated using a combination of synchrotron x-ray diffraction and nuclear resonant scattering. Conventional Mossbauer spectra were collected while the sample was heated in a resistive furnace. An analysis of the temperature evolution of the spectral shapes was used to identify the onset of fast electron hopping and determine the polaron hopping rate. Synchrotron x-ray diffraction measurements were carried out in the same temperature range. Reitveld analysis of the diffraction patterns was used to determine the temperature of sodium redistribution on the lattice. The diffraction analysis also provides new information about the phase stability of the system. The temperature evolution of the iron site occupancies from the Mossbauer measurements, combined with the synchrotron diffraction results give strong evidence for a relationship between the onset of fast electron dynamics and the redistribution of sodium in the lattice.

Measurements of activation barriers for polaron hopping gave fundamental insights about the correlation between electronic carriers and mobile ions. This work established that polaron-ion interactions can alter the local dynamics of electron and ion transport. These types of coupled processes may be common in many materials used for battery electrodes, and new details concerning the influence of polaron-ion interactions on the charge dynamics are relevant to optimizing their electrochemical performance.

I. Nuclear spin-internal-rotation-coupling. II. Fluorine spin-rotation interaction and magnetic shielding in fluorobenzene

Part I.

The interaction of a nuclear magnetic moment situated on an internal top with the magnetic fields produced by the internal as well as overall molecular rotation has been derived following the method of Van Vleck for the spin-rotation interaction in rigid molecules. It is shown that the Hamiltonian for this problem may be written

H_SR = Ῑ · M · Ĵ + Ῑ · M” · Ĵ”

Where the first term is the ordinary spin-rotation interaction and the second term arises from the spin-internal-rotation coupling.

The F¹⁹ nuclear spin-lattice relaxation time (T₁) of benzotrifluoride and several chemically substituted benzotrifluorides, have been measured both neat and in solution, at room temperature by pulsed nuclear magnetic resonance. From these experimental results it is concluded that in benzotrifluoride the internal rotation is crucial to the spin relaxation of the fluorines and that the dominant relaxation mechanism is the fluctuating spin-internal-rotation interaction.

Part II.

The radiofrequency spectrum corresponding to the reorientation of the F¹⁹ nuclear moment in flurobenzene has been studied by the molecular beam magnetic resonance method. A molecular beam apparatus with an electron bombardment detector was used in the experiments. The F¹⁹ resonance is a composite spectrum with contributions from many rotational states and is not resolved. A detailed analysis of the resonance line shape and width by the method of moments led to the following diagonal components of the fluorine spin-rotational tensor in the principal inertial axis system of the molecule:

F/Caa = -1.0 ± 0.5 kHz

F/Cbb = -2.7 ± 0.2 kHz

F/Ccc = -1.9 ± 0.1 kHz

From these interaction constants, the paramagnetic contribution to the F¹⁹ nuclear shielding in C₆H₅F was determined to be -284 ± ppm. It was further concluded that the F¹⁹ nucleus in this molecule is more shielded when the applied magnetic field is directed along the C-F bond axis. The anisotropy of the magnetic shielding tensor, σ_” - σ_⊥, is +160 ± 30 ppm.

I. The crystal structure of potassium bis(tricyanovinyl)amine. II. Nuclear magnetic resonance studies of alkali halide solutions. III. Elucidation of the intramolecular hydrogen bond in acetylacetone by the deuterium isotope effect on the chemical shift of the bridge hydrogen

Part I

Potassium bis-(tricyanovinyl) amine, K⁺N[C(CN)=C(CN)₂]₂^-, crystallizes in the monoclinic system with the space group Cc and lattice constants, a = 13.346 ± 0.003 Å, c = 8.992 ± 0.003 Å, B = 114.42 ± 0.02°, and Z = 4. Three dimensional intensity data were collected by layers perpendicular to b* and c* axes. The crystal structure was refined by the least squares method with anisotropic temperature factor to an R value of 0.064.

The average carbon-carbon and carbon-nitrogen bond distances in –C-CΞN are 1.441 ± 0.016 Å and 1.146 ± 0.014 Å respectively. The bis-(tricyanovinyl) amine anion is approximately planar. The coordination number of the potassium ion is eight with bond distances from 2.890 Å to 3.408 Å. The bond angle C-N-C of the amine nitrogen is 132.4 ± 1.9°. Among six cyano groups in the molecule, two of them are bent by what appear to be significant amounts (5.0° and 7.2°). The remaining four are linear within the experimental error. The bending can probably be explained by molecular packing forces in the crystals.

Part II

The nuclear magnetic resonance of ⁸¹Br and ¹²⁷I in aqueous solutions were studied. The cation-halide ion interactions were studied by studying the effect of the Li⁺, Na⁺, K⁺, Mg⁺⁺, Cs⁺ upon the line width of the halide ions. The solvent-halide ion interactions were studied by studying the effects of methanol, acetonitrile, and acetone upon the line width of ⁸¹Br and ¹²⁷I in the aqueous solutions. It was found that the viscosity plays a very important role upon the halide ions line width. There is no specific cation-halide ion interaction for those ions such as Mg⁺⁺, Di⁺, Na⁺, and K⁺, whereas the Cs⁺ - halide ion interaction is strong. The effect of organic solvents upon the halide ion line width in aqueous solutions is in the order acetone ˃ acetonitrile ˃ methanol. It is suggested that halide ions do form some stable complex with the solvent molecules and the reason Cs⁺ can replace one of the ligands in the solvent-halide ion complex.

Part III

An unusually large isotope effect on the bridge hydrogen chemical shift of the enol form of pentanedione-2, 4(acetylacetone) and 3-methylpentanedione-2, 4 has been observed. An attempt has been made to interpret this effect. It is suggested from the deuterium isotope effect studies, temperature dependence of the bridge hydrogen chemical shift studies, IR studies in the OH, OD, and C=O stretch regions, and the HMO calculations, that there may probably be two structures for the enol form of acetylacetone. The difference between these two structures arises mainly from the electronic structure of the π-system. The relative population of these two structures at various temperatures for normal acetylacetone and at room temperature for the deuterated acetylacetone were calculated.

Using measurements of muscle cell nuclear RNA with flow cytometry to improve assessment of larval condition of Walleye Pollock (Gadus chalcogrammus)

Nuclear RNA and DNA in muscle cell nuclei of laboratory-reared larvae of Walleye Pollock (Gadus chalcogrammus) were simultaneously measured through the use of flow cytometry for cell-cycle analysis during 2009–11. The addition of nuclear RNA as a covariate increased by 4% the classification accuracy of a discriminant analysis model that used cell-cycle, temperature, and standard length to measure larval condition, compared with a model without it. The greatest improvement, a 7% increase in accuracy, was observed for small larvae (<6.00 mm). Nuclear RNA content varied with rearing temperature, increasing as temperature decreased. There was a loss of DNA when larvae were frozen and thawed because the percentage of cells in the DNA synthesis cell-cycle phase decreased, but DNA content was stable during storage of frozen tissue.

A microbeam RBS analysis of low temperature direct-write inkjet deposited copper

Quantitative microbeam Rutherford backscattering (RBS) analysis with a 1.5 MeV 4He+ beam has determined limits on the purity of copper deposited on glass with a novel inkjet process. A tetravinyl silane tetrakisCu(I) 1,1,1,5,5,5-hexafluoroacetylacetonate (TVST[Cu]hfac) complex was heated to 70 °C and jetted onto the glass substrate through a piezoelectric ceramic print head in droplets about 0.5 mm diameter. The substrate temperature was 150 °C. Solid well-formed deposits resulted which have a copper content greater than about 90% by weight. The RBS spectra were analysed objectively using the DataFurnace code, with the assumption that the deposit was CuOx, and the validity of different assumed values of x being tested. The assumptions and the errors of the analysis are critically evaluated. © 2002 Elsevier Science B.V. All rights reserved.

Ultra-thin 242mAm fuel elements in nuclear reactors

There is a growing interest in using 242mAm as a nuclear fuel. The advantages of 242mAm as a nuclear fuel derive from the fact that 242mAm has the highest thermal fission cross section. The thermal capture cross section is relatively low and the number of neutrons per thermal fission is high. These nuclear properties make it possible to obtain nuclear criticality with ultra-thin fuel elements. The possibility of having ultra-thin fuel elements enables the use of these fission products directly, without the necessity of converting their energy to heat, as is done in conventional reactors. There are three options of using such highly energetic and highly ionized fission products. 1. Using the fission products themselves for ionic propulsion. 2. Using the fission products in an MHD generator, in order to obtain electricity directly. 3. Using the fission products to heat a gas up to a high temperature for propulsion purposes. In this work, we are not dealing with a specific reactor design, but only calculating the minimal fuel elements' thickness and the energy of the fission products emerging from these fuel elements. It was found that it is possible to design a nuclear reactor with a fuel element of less than 1 μm of 242mAm. In such a fuel element, 90% of the fission products' energy can escape.

Use of axially graded burnable boron for hot-spot temperature reduction in a pressurized water reactor core

Shortly after the loading of a pressurized water reactor (PWR) core, the axial power distribution in fresh fuel has already attained the characteristic, almost flat shape, typical of burned fuel. At beginning of cycle (BOC), however, the axial distribution is centrally peaked. In assemblies hosting uniform burnable boron rods, this BOC peaking is even more pronounced. A reduction in the axial peaking is today often achieved by shortening the burnable boron rods by some 30 cm at each edge. It is shown that a two-zone grading of the boron rod leads, in a representative PWR cycle, to a reduction of the hot-spot temperature of approximately 70 °C, compared with the nongraded case. However, with a proper three-zone grading of the boron rod, an additional 20 °C may be cut off the hot-spot temperature. Further, with a slightly skewed application of this three-zone grading, an additional 50 °C may be cut off. The representative PWR cycle studied was cycle 11 of the Indian Point 2 station, with a simplification in the number of fuel types and in the burnup distribution. The analysis was based on a complete three-dimensional burnup calculation. The code system was ELCOS, with BOXER as an assembly code for the generation of burnup-dependent cross sections and SILWER as a three-dimensional core code with thermal-hydraulic feedback.

Preliminary evaluation of a nuclear scenario involving innovative gas cooled reactors

In order to guarantee a sustainable supply of future energy demand without compromising the environment, some actions for a substantial reduction of CO 2 emissions are nowadays deeply analysed. One of them is the improvement of the nuclear energy use. In this framework, innovative gas-cooled reactors (both thermal and fast) seem to be very attractive from the electricity production point of view and for the potential industrial use along the high temperature processes (e.g., H 2 production by steam reforming or I-S process). This work focuses on a preliminary (and conservative) evaluation of possible advantages that a symbiotic cycle (EPR-PBMR-GCFR) could entail, with special regard to the reduction of the HLW inventory and the optimization of the exploitation of the fuel resources. The comparison between the symbiotic cycle chosen and the reference one (once-through scenario, i.e., EPR-SNF directly disposed) shows a reduction of the time needed to reach a fixed reference level from ∼170000 years to ∼1550 years (comparable with typical human times and for this reason more acceptable by the public opinion). In addition, this cycle enables to have a more efficient use of resources involved: the total electric energy produced becomes equal to ∼630 TWh/year (instead of only ∼530 TWh/year using only EPR) without consuming additional raw materials. © 2009 Barbara Vezzoni et al.

RBS STUDIES OF THE LATTICE DAMAGE CAUSED BY 1 MEV SI+ IMPLANTATION INTO AL0.3GA0.7AS/GAAS SUPERLATTICES AT ELEVATED-TEMPERATURE

The lattice damage accumulation in GaAs and Al0.3Ga0.7As/GaAs superlattices by 1 MeV Si+ irradiation at room temperature and 350-degrees-C has been studied. For irradiations at 350-degrees-C, at lower doses the samples were almost defect-free after irradiation, while a large density of accumulated defects was induced at a higher dose. The critical dose above which the damage accumulation is more efficient is estimated to be 2 x 10(15) Si/cm2 for GaAs, and is 5 x 10(15) Si/cm2 for Al0.8Ga0.7As/GaAs superlattice for implantation with 1.0 MeV Si ions at 350-degrees-C. The damage accumulation rate for 1 MeV Si ion implantation in Al0.3Ga0.7As/GaAs superlattice is less than that in GaAs.

Temperature-stimulated abnormal annealing of neutron-induced damage in high-resistivity silicon detectors

Neutron-irradiated high-resistivity silicon detectors have been subjected to elevated temperature annealing (ETA). It has been found that both detector full depletion voltage and leakage current exhibit abnormal annealing (or ''reverse annealing'') behaviour for highly irradiated detectors: increase with ETA. Laser induced current measurements indicate a net increase of acceptor type space charges associated with the full depletion voltage increase after ETA. Current deep level transient spectroscopy (I-DLTS) and thermally stimulated current (TSC) data show that the dominant effect is the increase of a level at 0.39 eV below the conduction band (E(c) - 0.39 eV) or a level above the valence band (E(v) + 0.39 eV). Candidates tentatively identified for this level are the singly charged double vacancy (V-V-) level at E(c) - 0.39 eV, the carbon interstitial-oxygen interstitial (C-i-O-i) level at E(v) + 0.36 eV, and/or the tri-vacancy-oxygen center (V3O) at E(v) + 0.40 eV.