Solid-state 17O NMR study of the electric-field-gradient and chemical shielding tensors in polycrystalline gamma-glycine

We report the first experimental determination of the carboxylate oxygen electric-field-gradient (EFG) and chemical shielding (CS) tensors in polycrystalline γ-glycine. Analysis of magic-angle spinning (MAS) and stationary ¹⁷O NMR spectra of [¹⁷O]-γ-glycine obtained at 9.4, 14.1, 16.4, and 18.8 T yields the magnitudes of the ¹⁷O EFG and CS tensors and the relative orientations between the two tensors. Extensive quantum chemical calculations at both the restricted Hartree–Fock and density functional levels have been performed to present the absolute tensor orientations in term of the molecular frame. We have demonstrated that ¹⁷O NMR tensor information could be unambiguously derived by the multiple field analyses of stationary ¹⁷O NMR spectra.     

One- and two-dimensional solid-state magic angle spinning NMR studies on the hydration process of layered sodium disilicate SKS-6

Three different kinds of silanols, which include isolated silanol, silanol I (with the hydroxyl proton bonded to an oxygen atom in the adjacent layer) and silanol II (with the hydroxyl proton bonded to the non-bridging oxygen at the same silicon atom), are generated during the hydration process of SKS-6 (δ-Na₂Si₂O₅). ¹H–¹H nuclear Overhauser enhancement spectroscopy reveals that the proton of silanol I has an effective chemical exchange or spin diffusion with the proton of hydrogen-bonded water, while the proton of silanol II is likely far away from the other proton-containing species. ²⁹Si magic angle spinning, ¹H→²⁹Si CP/MAS NMR and ¹H–²⁹Si phase-modulated Lee–Goldburg decoupled correlation experiments demonstrate that the local environments of the silicon sites in the final hydrated sample are mainly composed of Q² [(SiO)₂Si(OH)O⁻Na⁺], Q³ [(SiO)₃Si(OH) and (SiO)₃SiO⁻Na⁺] and Q⁴ [Si(OSi)₄] groups.     

An ab initio calculation of O and Si NMR parameters for SiO2 polymorphs

Ab initio molecular orbital calculations (Hartree–Fock, HF and density functional theories, DFTs) have been carried out for SiO₂ polymorphs coesite, low cristobalite, and α-quartz, in order to investigate the reliability of this method for predicting ²⁹Si and ¹⁷O nuclear magnetic resonance (NMR) properties of silicates. Oxygen- and silicon-centered clusters consisting of one (1T) to three tetrahedral (3T) shells (one to four atomic shells), taken from real crystal structure, have been investigated. It is found that for reasonable predication of both the ²⁹Si and ¹⁷O chemical shifts (δ_i^Si and δ_i^O), the minimum cluster is one that gives the correct second neighbors to the nucleus of interest. Both the δ_i^Si and δ_i^O have reached convergence with respect to cluster size at the OH-terminated two tetrahedral (2T) shell (three atomic shells around Si and four atomic shells around O) model. At convergence, the calculated δ_i^Si values agree well (within ±1 ppm) with experimental data. The calculated ¹⁷O electric field gradient (EFG)-related parameters also agree with experimental data within experimental uncertainties. The calculation also reproduces small differences in δ_i^O for O sites with similar tetrahedral connectivities, but shows deviations up to about 10 ppm in relative difference for O sites with different tetrahedral connectivities. The poor performance for the latter is mainly due to the approximations of the HF method. Our study thus suggests that the ab initio calculation method is a reliable mean for predicting ²⁹Si and ¹⁷O NMR parameters for silicates. Such an approach should find application not only to well-ordered crystalline phases, but also to disordered materials, by combining with other techniques, such as the molecular dynamics simulation method.     

Y型沸石脱铝机制和铝状态的NMR研究

对Y型沸石原粉及几种不同脱铝样品进行了几种不同NMR方法的测量,确定了不同处理过程的脱铝机制和骨架内外铝状态的变化,²⁹Si MAS NMR谱给出了骨架Si、Al分布的信息,反映了不同方法处理样品其脱铝机制的差异,据此可以控制Y沸石脱铝过程获得更高的硅铝比,²⁷Al MAS NMR谱、二维章动NMR及¹H-²⁷Al CP/MAS NMR测量表明:水热处理的Y沸石中存在4种不同的铝状态。综合²⁹Si和²⁷Al MAS NMR观测,可相当程度地推断Y型沸石分子筛脱铝改性所发生的内部过程。     

The Deep Potential Description of Backward-Angle Anomalous Behavior for a-Type Nucleus Elastic Scatterings

Within the framework of the optical model, the backward-angle anomalous behaviors of the angular distributions for the ¹⁶O+²⁴Mg and the ¹⁶O+²⁸Si elastic scatterings have been well described by using deep optical potentials. The excitation functions of elastic scattering for the ¹⁶O+²⁴Si system at θ _cm = 90° and 180° have also been reproduced well by using the same set of deep potential parameters. The results show that the effect of the deep potential resonance may be responsible for the backward-angle anomalous behavior.     

Determination of the (Na+) Sternheimer antishielding factor by 23Na NMR spectroscopy on sodium oxide chloride, Na3OCl

The (Na⁺) Sternheimer antishielding factor γ_∞ (Na⁺) was determined by ²³Na NMR spectroscopy on sodium oxide chloride, Na₃OCl. The quadrupolar coupling constant of the sodium ion in Na₃OCl was determined to QCC=11.34 MHz, which presents the largest coupling constant of a sodium nucleus observed so far. Applying a simple point charge model, the largest principal value of the electric field gradient at the sodium site was calculated to V_zz=−6.76762·10²⁰ V/m². From these values we calculated the (Na⁺) Sternheimer antishielding factor to γ_∞ (Na⁺)=−5.36. In sodium oxide, Na₂O, we observed an isotropic chemical shift of δ_CS=55.1 ppm, referenced to 1 M aqueous NaCl (δ=0 ppm).     

Hydrogen burning of O in the CNO cycle

The direct capture process in the ¹⁷O(p, γ)¹⁸F reaction has been used to determine the reduced proton widths of the states in ¹⁸F near the proton threshold. The observed upper limits on these widths are up to factors of 60 smaller than the previously assumed values implying a corresponding reduction of the stellar reaction rate for the ¹⁷O(p, )¹⁴N reaction. These results together with results from previous work lead to the conclusion that the CNO cycle is tricycling with the reactions ¹⁷O(p,γ)¹⁸F(β⁺ν)¹⁸O(p, )¹⁵N as the third cycle. The implications of these results on the equilibrium abundances of the elements synthesized in this cycle are discussed.     

The relativistic stripping model of (p, π) reactions in the Δ resonance region

The relativistic stripping model is presented for the (p, π⁺) reaction in the Δ-resonance region. The Dirac impulse approximation and a Dirac-Hartree calculation are used for the proton nucleus interaction and neutron bound state wave function respectively. The Δ-hole model is employed for the pion-nucleus interaction. This model is applied to the reaction ¹⁶O(p, π⁺)¹⁷O(g.s.).     

Vibrationally resolved band profiles for autoionisation of NO (cΠ) nℓλ (vR=0) Rydberg states into NO AΠ (vi=0, 1, 2) vibronic levels

Excitation spectra for dispersed VUV-fluorescence of NO (λ_fl=134–152 nm) were measured in the exciting-photon energy range between 16.9 and 24.8 eV using monochromatised synchrotron radiation at medium bandwidth of 29 meV. Fluorescence from A¹Π (v_i=0, 1, 2) vibronic NO⁺-levels and fluorescence from excited dissociation fragments NI (3s ²P_J) was observed simultaneously by recording the dispersed fluorescence with a monochromator–position-sensitive detector combination. The autoionisation of NO (c³Π) nℓλ (v_R=0) Rydberg levels into the NO⁺ A¹Π (v_i=0, 1, 2) vibronic levels was observed vibrationally resolved. Different Beutler–Fano profiles for autoionisation of one Rydberg level NO (c³Π) nℓλ (v_R=0) into the different vibronic NO⁺ A¹Π (v_i=0, 1, 2) levels are clearly visible. The dependence of the Beutler–Fano profiles on the quantum numbers n, ℓ, and λ of the Rydberg electron is discussed. For the direct photoionisation into the NO⁺ A¹Π (v_i=0, 1, 2) vibronic levels a non-Franck–Condon behaviour was observed.     

Solid state NMR characterisation of crystalline Na2OZrO2SiO2 phases

The NMR interactions of crystalline phases in the system Na₂O-ZrO₂-SiO₂ have been studied by a combination of static and magic angle spinning NMR methods for the first time. A full multinuclear (¹⁷O, ²³Na, ²⁹Si and ⁹¹Zr) approach has been employed that allows the phases to be clearly identified. NMR interactions such as ²⁹Si isotropic chemical shift correlate with the known structural units present. For ²³Na the different sites can often be distinguished on the basis of differing quadrupolar interactions.     

The effect of oxygen vacancy on the oxide ion mobility in LaAlO3-based oxides

The electrical property of (La_1−xSr_x)_1−z(Al_1−yMg_y)O_3−δ (LSAM; x≤0.3, y≤0.15 and z≤0.1) was measured using the DC four-probe method as a function of temperature (500–1000°C) and oxygen partial pressure (1–10⁻²² atm). Among LSAMs, (La_0.9Sr_0.1)AlO_3−δ showed the highest ionic conductivity, σ_i=1.3×10⁻² S cm⁻¹ at 900°C. A simultaneous substitution at A and B sites or A site deficiency is expected to create larger oxygen vacancy and higher ionic conductivity. However, it showed a negative effect. The effect of the vacancy increase did not effect monotonously the ionic conductivity. It was found that the concentration of oxygen vacancy, [V_O], influences not only the oxide ion conductivity, σ_i, but also the mobility, μ_v, of [V_O]. These properties exhibit a maximum at around [V_O]=0.05. With the increase in [V_O], the activation energy, E_a, of the ionic conduction dropped from 1.8 to ca. 1.0 eV at [V_O]=0.05 and became almost constant at [V_O]>0.05. The dependency of the pre-exponential term, μ⁰_v, and E_a on [V_O] was analyzed and their effect on μ_v and σ_i was discussed with respect to crystal structure and defect association. It was estimated that the crystal structure mainly governs these properties. The effect of defect association could not be ignored but is considered to be a complicated correlation.     

恒星氦燃烧关键反应12C(α,γ)16O天体物理S因子及其反应率

恒星氦燃烧阶段3α反应和12C（α,γ）16O反应相互竞争,两者的反应率共同决定了氦燃烧结束后12C与16O的丰度比,该比值是大质量恒星后继演化以及伴随的元素核合成过程的初始条件。目前,氦燃烧12C（α,γ）16O反应起始T₉=0.2处,天体物理模型要求的反应率的精确度要低于10%,然而尚未有实验或理论给出满足要求的结果。最为直接和可靠地获取12C（α,γ）16O反应率的方法,就是尽可能往低能区测量其天体物理S因子,然后通过理论外推到感兴趣的能区。为此基于经典的R-矩阵理论,建立了适用于低能核反应的多道、多能级的约化R-矩阵理论来拟合几乎所有可用的16O系统的实验数据。配合使用协方差统计和误差传播理论,拟合外推得到了客观的、内部自恰的和唯一性好的12C（α,γ）16O反应天体物理S因子。总的外推S因子STOT（0.3 MeV）=162.7±7.3 keV·b,理论上首次给出达到恒星演化与元素核合成模型的最低要求的S因子。基于计算给出的全能区的S因子,数值积分给出了温度位于0.04 6 T₉ 6 10的12C（α,γ）16O天体物理反应率。在T₉=0.2处,推荐的反应率为（7.83 ±0.35）×10-15 cm3mol-1s-1。During stellar helium burning, the rates of 3α and the 12C(α,γ)16O reaction, in competition with one another, determine the relative abundances of 12C and 16O in a massive star. The abundance ratio is the beginning condition of the following nucleosynthesis and star evolution of massive stars, which are extremely sensitive to the rate of 12C(α,γ)16O reaction at T₉=0.2. The most direct and trustworthy way to obtain the reaction rate of the 12C(α,γ)16O reaction is to measure the S factor for that reaction to as low energy as possible, and to extrapolate to energies of astrophysical interest. Based on a new multilevel and multichannel reduced R-matrix theory for applications in nuclear astrophysics, we have obtained an accurate and self-consistent astrophysical S factor of 12C(α,γ)16O, by a global fitting for almost all available experimental data of 16O system, with the coordination of covariance statistics and error-propagation theory. The extrapolated S factor of 12C(α,γ)16O was obtained with a recommended value STOT (0.3 MeV)=162.7±7.3 keV·b. And the reaction rates of 12C(α,γ)16O for stellar temperatures between 0.04 6 T₉ 6 10 are provided. At T₉=0.2, the reaction rate is (7.83 ±0.35)×10-15 cm3mol-1s-1, where stellar helium burning occurs.     

Comparison of the (17)O NMR spectra of zeolites LTA and LSX

¹⁷O NMR studies of various cation-exchanged LTA and LSX zeolites have shown similarities between the two systems. LSX samples containing divalent cations contain resonances with similar chemical shifts to those previously assigned to ‘bare’ framework oxygen atoms in Ca-LTA and Sr-LTA. The assignments are consistent with the trends seen in the spectra of monovalent cation-containing LSX and LTA zeolites, which show an increase in the average chemical shift with increasing cationic radius. The spectrum of Li-LSX, like Na-LSX, can be assigned based on the T–O–T bond angles. Gas sorption studies on Li-LSX are used to help identify the framework oxygen atoms that form the β-cages and demonstrate the sensitivity of the ¹⁷O shifts to gas loading.     

Stopping powers of CR-39 nuclear track material for Z=1−14 ions with 0.25–2.8 MeV/u

Experimental studies of the slowing down of ¹H, ⁴He, ⁷Li, ¹¹B, ¹²C, ¹⁴N, ¹⁶O, ²³Na, ²⁷Al and ²⁸Si ions in CR-39 nuclear track etch material in the ion energy range 0.25–2.8 MeV/u are presented. The ion stopping powers obtained are compared to the predictions of two recent semiempirical models for calculating ion stopping powers. The predictions are found to clearly underestimate the observed stopping powers for ⁷Li, ¹¹B, ¹²C, ²³Na, ²⁷Al and ²⁸Si ions.     

The (p, t) and (p, τ) reactions on O at 39.8 MeV

Differential cross sections have been measured at forward angles for (p, t) and (p, τ) transitions from ¹⁷O to the ⁻ ground states and lowest-energy ⁻ states in the ¹⁵O and ¹⁵N mirror nuclei. The data are compared with DWBA calculations using simple single-particle and single-hole wave functions. When the (p, t) and (p, τ) transitions are considered separately, the calculated and experimental ratios of the ⁻ integrated cross sections to the ⁻ integrated cross sections agree to within 30 %; however, the ratios of (p, τ) cross sections to the mirror state (p, t) cross sections are calculated to be about twice as large as actually measured. This experimentally observed reduction of the (p, τ) cross section relative to the (p, t) cross section can possibly be attributed to interference between the S = 0 and S = 1 components of the (p, τ) transitions.     

A (27)Al MAS NMR study of a sol-gel produced alumina: Identification of the NMR parameters of the theta-Al(2)O(3) transition alumina phase

²⁷Al MAS NMR has been used to study a sol–gel prepared alumina annealed at various temperatures. Two-field simulation of the sample heated to 1200 °C confirmed the presence of corundum, as suggested by XRD, and also the presence of nanocrystalline θ-Al₂O₃. ²⁷Al MAS NMR chemical shifts, quadrupolar coupling constants and asymmetry parameters are reported for the tetrahedral and octahedral aluminium sites within θ-Al₂O₃.     

Oxygen isotope effect of superconducting (Nd1−xCex)2CuO4−δ system

The effect of oxygen isotope substitution on the transition temperature T_c of a superconducting (Nd_1−xCe_x)₂CuO_4−δ system was studied, where the special synthetic method was taken to minimize ambiguous factors on the oxygen concentration and to guarantee the complete substitution of ¹⁶O by ¹⁸O. The isotope exponent in the relationship of T_c∝1/M was estimated to be less than 0.15 by magnetic susceptibility measurements.     

Effect of WO3 on the spectroscopic properties in Er/Yb co-doped bismuth–borate glasses

The spectroscopic properties of Er³⁺/Yb³⁺ co-doped Bi₂O₃–B₂O₃–WO₃ (BBW) glasses were analyzed and discussed. The effect of WO₃ content on the absorption spectra, the Judd–Ofelt parameters Ω_t (t=2, 4, 6), emission spectra and the lifetime of the ⁴I_13/2 level and the quantum efficiency of Er³⁺:⁴I_13/2→⁴I_15/2 transition were also investigated. With the substitution of WO₃ for B₂O₃, the measured lifetime of the ⁴I_13/2 level and the quantum efficiency of Er³⁺:⁴I_13/2→⁴I_15/2 transition increase from 0.98 to 1.31 ms and from 38.2% to 49.2%, respectively. The effective width of emission band and the emission cross-section both decrease slightly. And the emission spectra is analyzed via the different curve (σ_e−σ_a) of BBW glasses, the influence of OH⁻is also discussed.     

Deuterium conductivity, diffusion and implantation in Sr-doped LaYO3

A study of deuterium conductivity and diffusion in the oxide perovskite La_0.9Sr_0.1YO_3−δ is presented in this work. Deuterium ions were implanted into La_0.9Sr_0.1YO_3−δ (50 keV, 1×10¹⁶ atoms/cm²) and the corresponding deuterium depth profile was determined by SIMS and compared with a Monte Carlo simulation (TRIM96). This implant was used as a standard for the determination of deuterium concentration in a La_0.9Sr_0.1YO_3−δ sample pre-treated in D₂O atmosphere. In this way, it was fully confirmed that La_0.9Sr_0.1YO_3−δ incorporates water at high temperatures. The conductivity of La_0.9Sr_0.1YO_3−δ was measured in D₂O atmosphere and compared with other proton (deuteron) conductors. Concentration and conductivity data were used in conjunction to estimate the deuterium diffusivity and the constant of reaction of (heavy) water incorporation into LaYO₃. Some comments on the catalytic activity of this oxide are made.