Crystalline Aluminium Borates with the Mullite Structure: A <Superscript>11</Superscript>B and <Superscript>27</Superscript>Al Solid-State NMR Study

²⁷Al magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectra were acquired at 8.45, 14.1 and 16.45 T for a series of aluminium borates with the mullite structure (Al_6−x B _x O₉, where x has nominal values of 1 to 4) augmented with ²⁷Al multiple-quantum MAS NMR spectra at 8.45 T. Even though the ²⁷Al NMR spectra are complex, simulation of the combined set of data produced a relatively well-defined set of parameters (e.g., quadrupolar interaction, isotropic chemical shift, etc.) for each site. The ¹¹B MAS NMR spectra of the same compounds were also acquired at 14.1 T. Linear changes in the X-ray a-, b- and c-cell parameters with composition suggest that these compounds constitute a continuous series. Based on a Rietveld structural refinement of the compound synthesized as Al₄B₂O₉, the resulting site occupancies and relative site distortions allow the identification of particular sites with specific NM resonances. Changes in the ²⁷Al and ¹¹B MAS NMR spectra of the related compounds with x = 1–4 show at the lowest Al contents a greater degree of asymmetry in the Al sites of the octahedral chains. A fairly distorted cross-linking tetrahedral site, which persists throughout the composition range, is accompanied in the lower Al compositions by two 5-fold coordinated Al–O units which are replaced by two more-regular tetrahedral Al–O sites as the Al content increases. In the compounds of lowest Al composition (i.e., highest B content) both the tetrahedral and trigonal cross-linking sites are distinguishable, but as the Al content increases, the BO₄ units progressively disappear. Authors' address: Kenneth J. D. MacKenzie, School of Chemical and Physical Sciences, Victoria University of Wellington, P.O. Box 600, Wellington, New Zealand     

NMR Study of a Rare-Earth Aluminoborosilicate Glass with Varying CaO-to-Na<Subscript>2</Subscript>O Ratio

The effect of substituting two Na⁺ by one Ca²⁺ in a rare-earth aluminoborosilicate glass is investigated by multinuclear magic-angle spinning (MAS) and multiple-quantum (MQ)MAS nuclear magnetic resonance (NMR) spectroscopy. Quantitative analysis of the ²³Na and ²⁷Al MAS/MQMAS data along with the ¹¹B MAS NMR data provides complementary information enabling to cast light on different structural key points. A strong decrease of the N ₄ = BO₄/(BO₃ + BO₄) ratio is observed consecutively to this substitution, indicating that sodium is more favorable than calcium to the formation of BO₄ units. The experimental N ₄ ratio is compared to the Dell and Bray model prediction and it is shown that several adjustments, due to the presence in our glass of Nd and Zr, are necessary to obtain acceptable agreement with experimental data. ²⁹Si MAS NMR data also put in evidence an effect of the substitution on the polymerization degree. Glass in glass phase separation is clearly detected when the ratio of CaO to Na₂O is greater than 1 and a different evolution of NMR parameters is observed for the ratio of CaO to Na₂O being less than or equal to 1. Concerning aluminum charge compensation, it is demonstrated that, as long as no phase separation is detected, the negative charge of AlO₄ ⁻ entities is almost exclusively balanced by sodium cations. Finally, changes of the sodium ions organization within the glass network are also evidenced by spin–lattice relaxation and spin echo decay measurements. Authors' address: Thibault Charpentier, Laboratoire Claude Fréjacques, Service de Chimie Moléculaire, Commissariat à l'Energie Atomique Saclay, 91191 Gif-sur-Yvette cedex, France     

<Superscript>27</Superscript>Al NMR Study of the Structure and Dynamics of Natrolite

The temperature dependences of nuclear magnetic resonance and magic angle spinning nuclear magnetic resonance spectra of ²⁷Al nuclei in natrolite (Na₂Al₂Si₃O₁₀· 2H₂O) have been studied. The influence of water molecules and sodium ions mobility on the shape of the ²⁷Al NMR spectrum and framework dynamics have been discussed The temperature dependences of the spin–lattice relaxation times T₁ of ²⁷Al nuclei in natrolite have also been studied. It has been shown that the spin–lattice relaxation of the ²⁷Al is governed by the electric quadrupole interaction with the crystal electric field gradients modulated by translational motion of H₂O molecules in the natrolite pores. The dipolar interactions with paramagnetic impurities become significant as a relaxation mechanism of the ²⁷Al nuclei only at low temperatures (<270 K).     

NMR Studies of Heat-Induced Transitions in Structure and Cation Binding Environments of a Strontium-Saturated Swelling Mica

In this work, we combine ²⁷Al, ²⁹Si, ¹⁹F, and ²³Na magic-angle spinning (MAS) nuclear magnetic resonance (NMR) to characterize the structure and interlayer cation environments in a strontium-saturated member of the swelling mica family before and after a heat-induced collapse of the interlayer space. The ²⁷Al and ²⁹Si MAS NMR demonstrate that the sample consists mainly of swelling mica, though the composition does not match the ideal structural formula. Aluminum NMR also shows that a portion of the aluminum shifts from a tetrahedral to an octahedral coordination environment upon heating. Changes in the ²⁹Si and ¹⁹F NMR after heating are consistent with a structural rearrangement of the tetrahedral sheet to permit the binding of larger cations in the ditrigonal cavity. The ²³Na MAS NMR results indicate the presence of three unique sodium environments before and after heating. The heat-invariant resonance is consistent with the presence of sodium carbonate. The other two resonances are associated with interlayer sodium and reflect a migration of sodium to a dominantly anhydrous ditrigonal binding structure with heating. Quantitative elemental analysis and NMR data presented here suggest strontium is bound deep within the ditrigonal cavity of the collapsed micas. Authors' address: Karl T. Mueller, 104 Chemistry Building, Penn State University, University Park, PA 16802, USA     

<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.     

Multinuclear MAS NMR Investigation of Sol-Gel and Ball-Milled Nanocrystalline Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>

⁷¹Ga magic-angle spinning (MAS) nuclear magnetic resonance (NMR) has been used to characterize the structural evolution of nanocrystalline Ga₂O₃ samples prepared by sol-gel and ball-milling techniques. ²⁹Si and ²⁷Al MAS NMR have also been used to characterize silica and alumina Zener pinning phases. ⁷¹Ga NMR parameters are reported for the α- and β-Ga₂O₃ phases, and more tentatively for the δ-Ga₂O₃ phase. By simulating the octahedrally coordinated gallium NMR line of β-Ga₂O₃ using Gaussian distributions in χ_Q, the extent of disorder in the Ga₂O₃ crystallites has been quantified. The ball-milled samples contain much more inherent disorder than the sol-gel samples in the nano-phase, which was observed from simulations of the ⁷¹Ga MAS NMR spectra. The silica pinning phase produced highly crystalline and densely aggregated nanocrystalline Ga₂O₃, as well as the smallest nanocrystal sizes. Authors' address: Mark E. Smith, Department of Physics, University of Warwick, Coventry CV4 7AL, UK     

<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 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     

<Superscript>57</Superscript>Fe NMR study of multiferroic BiFeO<Subscript>3</Subscript>

The effects of the ⁵⁷Fe isotope content and high-frequency magnetic field amplitude h ₁ on the shape of the NMR spectrum of multiferroic BiFeO₃ at T = 4.2 K are studied by pulsed nuclear magnetic resonance. The NMR spectrum shape and transverse relaxation time T ₂ are found to depend strongly on the ⁵⁷Fe isotope content and h ₁ in multiferroic BiFeO₃ in the presence of a spatial spin-modulated structure of a cycloid type. In a sample with a high ⁵⁷Fe isotope content, the Suhl-Nakamura interaction contributes substantially to T ₂. When these dynamic effects are taken into account for analysis of the NMR spectrum shape, an undisturbed (without an anharmonicity effect) spatial spin-modulated structure of a cycloid type is shown to exist in BiFeO₃.     

<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.     

Distribution of <Superscript>28</Superscript>Si, <Superscript>29</Superscript>Si,and <Superscript>30</Superscript>Si isotopes under plastic deformation in subsurface layers of Si: B crystals

The redistribution of ²⁸Si, ²⁹Si, and ³⁰Si isotopes in subsurface layers of Si: B single crystals after their plastic deformation has been revealed. It has been found that the distribution profile of ²⁸Si and ²⁹Si isotopes becomes smoother after deformation, whereas the ³⁰Si isotope distribution remains unchanged. A change in the subsurface profile of the ²⁹SiO oxide is observed, which indicates the migration of the ²⁹Si isotope in the composition of oxygen complexes during plastic deformation.     

Al and Si MAS NMR investigations of cordierite glass, μ- and α-cordierite

²⁷Al and ²⁹Si Magic-Angle Spinning NMR results are reported for conventionally prepared glass of cordierite stoichiometry (2MgO · 2Al₂O₃ · 5SiO₂), the metastable high-quartz solid solution (μ-cordierite) and the high-temperature polymorph of cordierite (α-cordierite). Both, ²⁷Al two-dimensional (2D) quadrupole nutation experiments and ²⁷Al satellite transition spectroscopy (SATRAS) have been applied to identify two different tetrahedrally-coordinated aluminium sites (AlO₄). SATRAS has been used to extract the quadrupole interaction parameters and their distribution, the isotropic chemical shifts and the relative populations of the different Al sites. Both, the ²⁷Al and ²⁹Si NMR results, lead to the conclusion that a perfect Si/Al disorder does not exist in these investigated cordierite samples.     

Near infrared lights emission of <Superscript>40</Superscript>Ar<Superscript>16+</Superscript> impacting on metal surfaces

The highly charged ion ⁴⁰Ar¹⁶⁺ with the velocity (kinetic energy E _K=150 keV, velocity V=8.5×10⁵ m/s) smaller than Bohr velocity (V _Bohr=2.9×10⁶ m/s) was found to hove impacts on the surfaces of metals Ni, Mo, Au and Al, and the Ar atomic infrared light lines and X-rays spectra were simultaneously measured. The experimental results show that the highly charged ion that captures electrons is neutralized, and the multiply-excited hollow atom forms. The hollow atom cascade decay radiates lights from infrared to X-ray spectrum. The intensity of infrared lights shows that the metallic work functions play an important role in the neutralization process of highly charged ions during their interaction with metallic surfaces, which verifies the classical over-the-barrier model. Supported by the National Natural Science Foundation of China (Grant No. 10574132), the Natural Science Foundation of Shaanxi Province (Grant No. 2007A05) and the Talents Introduction Project of Xianyang Normal University (Grant No. 05XSYK103)     

Fast Si magic-angle-spinning NMR acquisitions by RAPT-CP Al → Si polarization transfer

Using enhancement of the ²⁷Al central-transition magnetization by applying RAPT prior to ²⁷Al → ²⁹Si cross-polarization, we demonstrate fast acquisition of ²⁹Si one-dimensional MAS and two-dimensional ²⁷Al–²⁹Si HETCOR spectra on a new sialon phase Ba₂Al₃Si₉N₁₃O₅.     

17O DOR and other solid-state NMR studies concerning the basic properties of zeolites LSX

We demonstrate complementary ¹H, ¹⁷O, ²⁷Al and ²⁹Si measurements for basic low-silica-X zeolites, which were unloaded and pyrrole and formic acid-loaded. It was found that the acid–base-system is not stabile, if the loading exceeds one pyrrole molecule or two formic acid molecules per supercage.¹⁷O DOR NMR spectra exhibit at least four lines, which are broadened by a distribution of chemical shifts in a similar extend as the ²⁹Si MAS NMR spectra are broadened by distribution of Si–O–Al angles. A strong cation influence upon ¹⁷O shifts was observed. But there was no strong influence of the acid molecules on the mean value of the ¹⁷O shift of the spectra.     

Total strength of the magnetic dipole resonance in <Superscript>31</Superscript>P

The γ decay of the resonance-like structure observed in the ³⁰Si(pγ)³¹P reaction in the energy range E _p = 1.4–2.7 MeV of accelerated protons has been investigated. The excitation function of this reaction and the spectra and angular distributions of the γ rays formed in the decay of resonances with E _p = 1482, 2350, and 2505 keV have been measured. The M1 resonance on the ground and the first excited states of ³¹P with E _p = 1266 keV is identified. The total strength of the M1 resonance on the ground state of this nucleus is determined. The position and total strength of this resonance on the ground state are explained taking into account pairing forces.     

<Superscript>1</Superscript>H and<Superscript>13</Superscript>C chemical shift assignments and stereochemistry of matrine and oxymatrine

Matrine and oxymatrine were extracted fromSophora flavescens, and their¹H and¹³C nuclear magnetic resonances (NMR) were unambiguously assigned by a combination of different two-dimensional 2-D¹H-¹³C and¹H-¹H correlation experiments of HMQC, HMQC-TOCSY and MAXY. The technique of using those experiments to make the assignment of the heavily overlapped spectrum is demonstrated. The coupling constants of matrine were measured by 2-DJ-resolved spectrum and 1-D spectra extracted from the slices of 2-D MAXY spectrum. The stereochemistry of the titled compounds was established from the NMR spectroscopy.     

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).     

Dynamical properties of ions confined within dense dispersions of charged anisotropic colloids : A <Superscript>23</Superscript>Na quadrupolar NMR study

We used ²³Na quadrupolar NMR spectroscopy and relaxation measurements to determine the mobility of the sodium counterions confined within dense aqueous dispersions of synthetic Laponite clays as a model of charged anisotropic nano-composite colloids. The lineshape analysis of the ²³Na spectra and the measurements of the Hahn echo attenuation are used to determine the critical clay concentration corresponding to the nematic organisation of the dispersion. As validated by numerical simulations of the ion diffusion within partially oriented nematic dispersion of the anisotropic colloids, the angular variation of the apparent relaxation rates is interpreted as an indice of degree of ordering of the dispersion.     

Indication for hyperdeformed cluster states in <Superscript>233</Superscript>Th

An activation technique was used to investigate relative yields of fission products from the reaction ²³²Th(n, f ) for neutron energies between 1.3 and 1.8MeV covering the region around the first hyperdeformed resonances. Intensities of characteristic γ-ray transitions were analyzed to search for changes in the mass distribution for neutron energies corresponding to the resonances and below the resonances. Relative increases in yield between 7 and 23% are observed for A ≈ 100 and 132 in the resonance region around 1.6MeV. It is proposed that the yield enhancement of daughter nuclei of the preformed fragments ¹³²Sn and ¹⁰¹Zr arises from cold fission of a di-cluster configuration. The experimental results support theoretical predictions for the existence of hyperdeformed octupole shapes based on the di-nuclear configuration ¹³²Sn + ¹⁰¹Zr.