<Superscript>29</Superscript>Si, <Superscript>27</Superscript>Al, <Superscript>1</Superscript>H and <Superscript>23</Superscript>Na MAS NMR Study of the Bonding Character in Aluminosilicate Inorganic Polymers

²⁹Si, ²⁷Al, ¹H and ²³Na solid-state magic-angle spinning (MAS) nuclear magnetic resonance (NMR) has been used to relate nominal composition, bonding character and compressive strength properties in aluminosilicate inorganic polymers (AIPs). The ²⁹Si chemical shift varies systematically with Si-to-Al ratio, indicating that the immediate structural environment of Si is altering with nominal composition. Fast ¹H MAS and ²⁹Si T _SiH/T _1ρ relaxation measurements demonstrated that occluded pore H₂O mobility within the disordered cavities is slow in comparison with H₂O mobility characteristics observed within the ordered channel structures of zeolites. The ²⁷Al MAS NMR data show that the Al coordination remains predominantly 4-coordinate. In comparison with the ²⁹Si MAS data, the corresponding ²⁷Al MAS line shapes are relatively narrow, suggesting that the AlO₄ tetrahedral geometry is largely unperturbed and the dominant source of structural disorder is propagated by large distributions of Si–O bond angles and bond lengths. Corresponding ²³Na MAS and multiple-quantum MAS NMR data indicate that Na speciation is dominated by distributions of hydration states; however, more highly resolved ²³Na resonances observed in some preparations supported the existence of short-range order. New structural elements are proposed to account for the existence of these Na resonances and an improved model for the structure of AIPs has also been proposed. Authors' address: John V. Hanna, NMR Facility, Institute of Materials and Engineering Science, Lucas Heights Research Laboratories, Australian Nuclear Science and Technology Organisation, Private Mail Bag 1, Menai, NSW 2234, Australia     

<Superscript>23</Superscript>Na spin-lattice relaxation in powder Rochelle salt

The temperature dependence of ²³Na spin-lattice relaxation in the polycrystalline Rochelle salt was studied by NMR within the range from 235 to 320 K covering both Curie points. The spin-relaxation time t ₁ versus temperature curve showed noticeable dips near the phase transitions against the background of the regular decrease in the relaxation time upon increasing temperature. The dips observed were ascribed to critical contributions to sodium spin-lattice relaxation caused by the slowdown of the correlation time for one of two relaxation modes in the Rochelle salt. The ²³Na NMR parameters were also measured for the melted Rochelle salt. This article was submitted by the authors in English.     

<Superscript>23</Superscript>Na and <Superscript>27</Superscript>Al NMR Study of Structure and Dynamics in Mordenite

Temperature dependencies of ²⁷Al and ²³Na nuclear magnetic resonance spectra and spin–lattice relaxations in mordenite have been studied in static and magic angle spinning regimes. Our data show that the spin–lattice relaxations of the ²³Na and ²⁷Al nuclei are mainly governed by interaction of nuclear quadrupole moments with electric field gradients of the crystal, modulated by translational motion of water molecules in the mordenite channels. At temperatures below 200 K, the dipolar interaction of nuclear spins with paramagnetic impurities becomes an important relaxation mechanism of the ²³Na and ²⁷Al nuclei.     

<Superscript>23</Superscript>Na NMR in binary lithium-sodium cobaltite

Li_0.48Na_0.35CoO₂ lithium-sodium cobaltite was studied by means of wide-line ²³Na and ⁷Li NMR. A series of quantum-chemical calculations allowed to us determine the optimum positions of Li and Na atoms, to construct a map of the densities of electronic states near the Fermi level, and to estimate the electric field gradient on the Na nuclei. The results from these calculations are compared with experimental data from NMR and X-ray photoelectron spectroscopy     

Orbital glass and spin glass states of <Superscript>3</Superscript>He-A in aerogel

Glass states of superfluid A-like phase of ³He in aerogel induced by random orientations of aerogel strands are investigated theoretically and experimentally. In anisotropic aerogel with stretching deformation two glass phases are observed. Both phases represent the anisotropic glass of the orbital ferromagnetic vector Ηthe orbital glass (OG). The phases differ by the spin structure: the spin nematic vector \(\hat d\) can be either in the ordered spin nematic (SN) state or in the disordered spin-glass (SG) state. The first phase (OG-SN) is formed under conventional cooling from normal ³He. The second phase (OG-SG) is metastable, being obtained by cooling through the superfluid transition temperature, when large enough resonant continuous radio-frequency excitation is applied. NMR signature of different phases allows us to measure the parameter of the global anisotropy of the orbital glass induced by deformation.     

Magnetic Resonance Imaging on Sodium Nuclei: Potential Medical Applications of <Superscript>23</Superscript>Na MRI

Sodium is a key element in a living organism. The increase of its concentration is an indicator of many pathological conditions. ²³Na magnetic resonance imaging (MRI) is a quantitative method that allows to determine the sodium content in tissues and organs in vivo. This method has not yet entered clinical practice widely, but it has already been used as a clinical research tool to investigate diseases such as brain tumors, breast cancer, stroke, multiple sclerosis, hypertension, diabetes, ischemic heart disease, osteoarthritis. The active development of the ²³Na MRI is promoted by the growth of available magnetic fields, the expansion of hardware capabilities, and the development of pulse sequences with ultra-short echo time.     

Recent results on hyperpolarized<Superscript>3</Superscript>He−<Superscript>4</Superscript>He liquid mixtures

Laser optical pumping in low magnetic field provides very high nuclear polarizations in gaseous helium mixtures, and is used to prepare polarized liquid. Wall relaxation in glass cells is effiently reduced using cesium coatings, and bulk longitudinal relaxation times are measured. In highly magnetized samples, dipolar fields control the spin dynamics in anisotropic volumes and weak external magnetic field inhomogeneities. Long lived magnetostatic modes are observed by pulsed NMR. Detailed analysis of their frequency and damping gives information on magnetization density and spin diffusion coefficient in polarized mixtures. Experiments are performed above 0.2 K on mixtures with³He concentrations of order a few percents or larger. When phase separation occurs, the³He-rich phase retains a high polarization.     

<Superscript>17</Superscript>O and<Superscript>23</Superscript>Na nuclear quadrupole double resonance of sodium formate and sodium acetate

The¹⁷O and²³Na nuclear quadrupole resonance spectra of powdered sodium formate and sodium acetate have been determined at room temperature by proton-¹⁷O and proton-²³Na double resonance. All¹⁷O sites have been found to be chemically equivalent. The nonzero value of the asymmetry parameter of the electric field gradient tensor at the¹⁷O site shows that the electron density distribution is not cylindrically symmetric around the C−O bond axis.     

Elastic and inelastic scattering of 800-MeV protons on <Superscript>16</Superscript>O and <Superscript>20</Superscript>Ne nuclei

Differential cross sections and polarization observables for the elastic and inelastic scattering of 800-MeV protons on ¹⁶O and ²⁰Ne nuclei are calculated on the basis of the theory of multiple diffractive scattering and the α-cluster model involving dispersion. The single-particle nucleon-density distributions obtained within the α-cluster model involving dispersion are used in the calculations. The differential cross sections and polarization calculated for elastic and inelastic p¹⁶O and p²⁰Ne scattering are compatible with available experimental data. The spin-rotation functions calculated for elastic p¹⁶O and p²⁰Ne scattering within the independent-nucleon model differ qualitatively from their counterparts calculated within the α-cluster model involving dispersion.     

Density-functional calculation of the quadrupole splitting in the <Superscript>23</Superscript>Na NMR spectrum of the ferric wheel Na@Fe<Subscript>6</Subscript>(tea)<Subscript>6</Subscript><Superscript>+</Superscript> for various broken-symmetry states of the Heisenberg spin model

The quadrupole splitting in the ²³Na nuclear magnetic resonance (NMR) spectrum of the hexanuclear ferric wheel Na@Fe₆(tea)₆ ⁺ has been computed via an evaluation of the electric-field gradient (EFG) at the Na nucleus in the framework of density-functional theory (DFT). The simulated spectrum is compared with experimental data. A total of 2⁶ = 64 Kohn-Sham determinants (a number that reduces to eight symmetry-unique determinants due to the high S₆ symmetry of the ferric wheel) with six localised high-spin Fe(III) centres (S = 5/2) could be optimised in a self-consistent manner, and the corresponding DFT energies of all of these (broken-symmetry) determinants coincide almost perfectly according to the Ising Hamiltonian solutions, especially when the energy is computed from the B3LYP functional. The EFG at the Na atom does not depend much on the specific Kohn-Sham determinant but depends on the geometry of the ferric wheel and on the basis set used in the DFT calculations (particularly with regard to the atomic functions on the Na atom).     

Nuclear level densities in <Superscript>47</Superscript>V, <Superscript>48</Superscript>V, <Superscript>49</Superscript>V, <Superscript>53</Superscript>Mn,and <Superscript>54</Superscript>Mn from neutron evaporation spectra

The spectra of neutrons from the (p, n) reactions on ⁴⁷Ti, ⁴⁸Ti, ⁴⁹Ti, ⁵³Cr, and ⁵⁴Cr nuclei were measured in the proton-energy range 7–11 MeV. The measurements were performed with the aid of a fast-neutron spectrometer by the time-of-flight method over the base of the EGP-15 tandem accelerator of the Institute for Physics and Power Engineering (IPPE, Obninsk). Owing to a high resolution and a high stability of the time-of-flight spectrometer used, low-lying discrete levels could be identified reliably along with a continuum section of neutron spectra. An analysis of measured data was performed within the statistical equilibrium and preequilibrium models of nuclear reactions. The relevant calculations were performed by using the exact formalism of Hauser-Feshbach statistical theory supplemented with the generalized model of a superfluid nucleus, the back-shifted Fermi gas model, and the Gilbert-Cameron composite formula for the nuclear level density. The nuclear level densities for ⁴⁷V, ⁴⁸V, ⁴⁹V, ⁵³Mn, and ⁵⁴Mn were determined along with their energy dependences and model parameters. The results are discussed together with available experimental data and recommendations of model systematics.     

Absorption line strengths of <Superscript>15</Superscript>NH<Subscript>3</Subscript> in the near infrared spectral region

We present initial results of an investigation of the near infrared absorption spectrum of ¹⁵NH₃ between 6468 and 6692 cm⁻¹. A widely tunable external cavity diode laser is used in a direct absorption setup to determine the line positions and line strengths of several lines in that spectral range. Line data measurements on a ¹⁴NH₃ sample are used for validation of the setup by comparison of the results with available literature data. The presented overview measurements on absorption lines of ¹⁵NH₃ have been performed to serve as a starting point for candidate line selection for prospective isotopic ratio measurements of ¹⁴NH₃ and ¹⁵NH₃.     

<Superscript>55</Superscript>Mn spin relaxation with the participation of mobile carriers in doped perovskites

Analytical expressions are derived for the rates of longitudinal and transverse nuclear spin relaxation under conditions of fast modulation of the magnitude and direction of a hyperfine field induced by unpaired electrons of an ion. The results obtained are used to explain the data available in the literature on the ⁵⁵Mn spin relaxation in the ferromagnetic metallic phase of doped perovskites, in which the modulation of the hyperfine field is caused by the hopping of e _g electrons between Mn³⁺ and Mn⁴⁺ ions. It is demonstrated that, within this model, the rates of longitudinal and transverse relaxation are characterized by the same temperature dependence and their ratio is independent of temperature, which is in agreement with the experimental data.     

Polarization phenomena in the intermediate energy elastic deuteron scattering from <Superscript>16</Superscript>C and <Superscript>16</Superscript>O nuclei

A model based on the multiple diffraction scattering theory and the α-cluster model with dispersion of target nuclei is proposed for describing the behavior of observables for the elastic deuteron scattering from ¹²C and ¹⁶O nuclei at intermediate energies. Differential cross-sections and analyzing powers calculated within this approach for incident-deuteron energies of 400 and 700 MeV are in a reasonable agreement with experimental data.     

Magneto-optical trap and mass-separator system for the ultra-sensitive detection of <Superscript>135</Superscript>Cs and <Superscript>137</Superscript>Cs

We report the first magneto-optical trapping of radioactive ¹³⁵Cs and ¹³⁷Cs and a promising means for detecting these isotopes at ultra-sensitive levels by coupling a magneto-optical trap (MOT) to a mass separator. A sample containing both isotopes was placed in the source of a mass separator, ionized, mass-separated, and implanted in a Zr foil within the trapping cell. After implantation, atoms were released from the foil by inductive heating and then captured in a MOT that used large-diameter beams and a dry-film-coated cell to achieve high trapping efficiency. Trapped-atom numbers in the case of either isotope ranged from 10⁴ to 10⁷, as determined from the MOT fluorescence signal. Over this trapped-atom range, the MOT fluorescence signal was found to increase linearly with the number of atoms implanted in the foil and without isotopic bias to within 4%. In principle, this method can then provide a measurement of the ¹³⁷Cs/¹³⁵Cs ratio accurate to within 4% through the direct ratio of MOT fluorescence signals. The fluorescence signal from stable ¹³³Cs, when implanted and released from the foil, was suppressed relative to MOT signals by more than seven orders of magnitude when the system was tuned to trap ¹³⁵Cs or ¹³⁷Cs. When combined with the isotopic selectivity of ≥10⁵ for the mass separator, the overall suppression of ¹³³Cs is expected to exceed 10¹². At present our system delivers atoms from sample to MOT with an efficiency of 0.5%, has a trapped-atom detection limit of 4000 atoms, and achieves a sample-detection sensitivity of one million atoms. Received: 23 August 2002 / Published online: 8 January 2003 RID="*" ID="*"Corresponding author. Fax: +1-505/667-0440, E-mail: mdd@lanl.gov     

Nonradiative relaxation of photoexcited O<Stack><Subscript>1</Subscript><Superscript>0</Superscript></Stack> centers in glassy SiO<Subscript>2</Subscript>

The processes involved in the excited-state relaxation of hole O ₁ ⁰ centers at nonbridging oxygen atoms in glassy SiO₂ were studied using luminescence, optical absorption, and photoelectron emission spectroscopy. An additional nonradiative relaxation channel, in addition to the intracenter quenching of the 1.9-eV luminescence band, was established to become operative at temperatures above 370 K. This effect manifests itself in experiments as a negative deviation of the temperature-dependent luminescence intensity from the well-known Mott law and is identified as thermally activated external quenching with an energy barrier of 0.46 eV. Nonradiative transitions initiate, within the external quenching temperature interval, the migration of excitation energy, followed by the creation of free electrons. In the final stages, this relaxation process becomes manifest in the form of spectral sensitization of electron photoemission, which is excited in the hole O ₁ ⁰ -center absorption band.     

The low-energy dipole structure of <Superscript>232</Superscript>Th , <Superscript>236</Superscript>U and <Superscript>238</Superscript>U actinide nuclei

In this study, I^p = 1⁺\ensuremath I^{\pi} = 1^{+} and I^p = 1^-\ensuremath I^{\pi} = 1^{-} dipole mode excitations are systematically investigated within the rotational and translational + Galilean invariant quasiparticle random-phase approximation for ²³²Th , ²³⁶U , and ²³⁸U actinide nuclei. It is shown that the investigated nuclei reach a B(M1) strength structure, which corresponds to the scissors mode. The calculated mean excitation energies as well as the summed B(M1) value of the scissors mode excitations are consistent with the available experimental data. The results of calculations indicate large differences to the rare-earth nuclei as is the case for the experiment: a doubling of the observed dipole strengths and a shift of the energy centroid to the lower energies by about 800keV. The calculations indicate the presence of a few prominent negative-parity K^p = 1^-\ensuremath K^{\pi} = 1^{-} states in the 2.0-4.0MeV energy interval. The occurrence of the negative-parity dipole states with the rather high B(E1) value less than 4MeV shows the necessity of explicit parity measurements for the correct determination of the scissors mode strength in ²³²Th , ²³⁶U , and ²³⁸U isotopes.     

<Superscript>210</Superscript>Pb and <Superscript>210</Superscript>Po determination in environmental samples using liquid scintillation counting and alpha spectrometry

A simple radiochemical procedure has been developed to determine ²¹⁰Pb and ²¹⁰Po in environmental samples from the same matrix. Sediment samples are decomposed by leaching with mineral acids or by microwave digestion, while water samples are pre-concentrated. One part of the resulting solution, spiked with ²⁰⁹Po, is used for ²¹⁰Po determination by spontaneous deposition onto nickel disks (α-spectrometry). The other part is assayed for ²¹⁰Pb, separating the Pb either by anion-exchange (sediment samples), or by solvent extraction (water samples). The ²¹⁰Pb source is finally prepared by precipitation as oxalate and the chemical recovery determined by gravimetry. The ²¹⁰Pb activity concentration is determined by liquid scintillation. A standard sediment sample supplied by IAEA and spiked water samples were analysed to check the procedure. The ²¹⁰Pb and ²¹⁰Po measurements agreed well with the certifications, deviations being less than 10%. The mean recoveries for Pb and Po were (70±12)% and (77±8%) for sediments, and (70±10)% and (81±7)% for waters, respectively.     

Angular dependence of the relaxation times of <Superscript>139</Superscript>La nuclei in La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript>

Relaxation of the magnetization of ¹³⁹La nuclei is considered in lanthanum manganites, which are materials with anisotropic interactions of localized electronic spins, namely, the Dzyaloshinski?-Moriya interactionand the interaction with a crystal field. Expressions are derived for the relaxation times of the longitudinal and transverse components of the nuclear magnetization, and the angular dependences of these relaxation times are found for the La_0.95Sr_0.05MnO₃ compound. In contrast to electronic relaxation, the anisotropy of nuclear relaxation contains a contribution from the shift in the electron Zeeman frequency. The theoretically calculated numerical values of the nuclear relaxation times and their ratios correspond to the range of experimental values in the compounds studied. The results can be of importance for designing devices based on these materials and for further investigation.     

Evolution of NaNO<Subscript>2</Subscript> in porous matrices

NMR and dielectric studies of NaNO₂ loaded into an SBA-15 mesoporous matrix are reported. The spin-lattice relaxation rate and the ²³Na NMR line shift, as well as the permittivity, were measured within a broad temperature interval including the ferroelectric phase transition in NaNO₂. The phase transition temperature of sodium nitrite in as-prepared samples was shown to differ substantially from that characteristic of a bulk crystal. The permittivity grows strongly in the vicinity of the phase transition. Heating a sample causes the properties of NaNO₂ embedded in pores to gradually approach those of bulk crystals.