Experimental and theoretical 31P and 77Se nuclear magnetic shielding tensors for bis(dineopentoxyphosphorothioyl) diselenide

An intergrown crystal of two phases of bis(dineopentoxyphosphorothioyl) diselenide 1 was investigated by goniometer ³¹P NMR. From the angular dependence of the chemical shift, the tensors of a triclinic and a monoclinic phase were determined. The principal values σ₁₁, σ₂₂, and σ₃₃ of the absolute nuclear magnetic shielding tensors for the triclinic phase are 134.1, 227.2, and 375.5 ppm and for the monoclinic phase are 132.4, 227.8, and 374.2 ppm, respectively. In both cases, the principal axis 3 of the ³¹P tensor is directed nearly along the P=S bond and the principal axis 2 is nearly perpendicular to the S=P—Se plane. Calculations of the ³¹P and ⁷⁷Se nuclear magnetic shielding tensors were performed for molecules of both phases of 1 and for model compounds by the sum-over-states density functional perturbation theory IGLO method. The rms distances between calculated and experimental ³¹P NMR icosahedral tensor values σ_j(j = 1,…,6) amount to 17–21 ppm. The calculated and experimental orientations of the ³¹P principal axes show a maximum difference of 5° and rms distances of 3.2 and 3.3°. For the principal value σ₃₃ of the selenium shielding tensor the agreement between calculated and experimental values is satisfactory, but the calculated values σ₁₁ and σ₂₂ are distinctly too small. Calculations for a model compound in which the methyl groups of the neopentoxy residue are substituted by protons lead practically to the same results.     

通过超宽139La固体核磁共振波谱研究层状La(OH)2NO3

层状稀土氢氧化物是一类新型的稀土功能材料，本文采用固体核磁共振（SSNMR）方法研究了同时具备离子交换能力和非线性光学特性的层状La（OH）₂NO₃化合物，探讨了通过四极核CPMG（QCPMG）脉冲序列和变频谱图采集获取超宽¹³⁹La SSNMR谱图的方法，并描述了适用于此类实验的滤波方程和谱图重建方法.重建谱图同时包含四极核中心跃迁和卫星跃迁信息，本文使用QUEST软件对超宽¹³⁹La NMR谱图进行了模拟，获取的四极耦合常数C_Q和非对称因子η_Q均与CASTEP密度泛函理论计算值高度吻合.SSNMR实验结果证实层状La（OH）₂NO₃化合物属于非中心对称结构（P2₁），解决了对其结构长期以来存在的争论.     

59Co, 23Na NMR and electric field gradient calculations in the layered cobalt oxides NaCoO2 and HCoO2

⁵⁹Co and ²³Na NMR has been applied to the layered cobalt oxides NaCoO₂ and HCoO₂ at three different magnetic field strengths (4.7, 7.1 and 11.7 T). The ⁵⁹Co and ²³Na quadrupole and anisotropic shift tensors have been determined by iterative fitting of the NMR line shapes at the three magnetic field strengths. Due to the large ⁵⁹Co quadrupole interaction in NaCoO₂, a frequency-swept irradiation procedure was used to alleviate the limited bandwidth of the excitation. While the ⁵⁹Co and ²³Na shift and quadrupole coupling tensors in NaCoO₂ are found to be coincident and axially symmetric in agreement with the crystal symmetry requirements, the fits of the ⁵⁹Co NMR spectra clearly show the presence of structural disorder in HCoO₂. The ²³Na chemical shift anisotropy can be reproduced by shift tensor calculations using a point dipole model and considering that the magnetic susceptibility in NaCoO₂ is due to Van Vleck paramagnetism for Co³⁺. Electric field gradient calculations using either the empirical point charge model or the ab initio full potential-linearized augmented plane wave method are compared with the experimental NMR data.     

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.     

93Nb NMR chemical shift scale for niobia systems

⁹³Nb solid-state NMR spectra of a series of inorganic niobates with Nb in different oxygen coordination environments were measured. For all studied compounds the chemical shielding and quadrupole tensor parameters were determined using conventional and ultrahigh field NMR facilities, ultrahigh speed MAS, DQ STMAS, solid-echo and computer modeling. It has been demonstrated that the ⁹³Nb isotropic chemical shift is sensitive to the coordination number of Nb sites. For the first time the ⁹³Nb NMR chemical shift scale for NbO_x polyhedra in solid materials has been proposed: for four-coordinated Nb sites, the isotropic shifts occur from −650 to −950 ppm; five-coordinated Nb sites have the isotropic shifts in the range of –900 to –980 ppm; for six-coordinated Nb sites the isotropic shifts vary from −900 to −1360 ppm; the shifts from −1200 to −1600 ppm are typical for seven-coordinated Nb sites; for eight-coordinated Nb sites the shifts are higher than −1400 ppm. The possible correlation between the value of the isotropic chemical shift and the ionic character of the NbO_x–MO_y polyhedra association has been suggested. The magnitude of the ⁹³Nb quadrupole coupling constant depends on the local symmetry of Nb sites and may vary from hundreds of kHz to hundreds of MHz.     

Microscopic measurements in La-NQR of the ternary carbide superconductor LaNiC2

¹³⁹La-NQR measurements have been carried out in the ternary carbide superconductor LaNiC₂. The nuclear quadrupole frequency and the asymmetry parameter of ¹³⁹La in LaNiC₂ were estimated to be about 1.9 MHz and 0, respectively. In the normal state, the nuclear spin relaxation rate (1/T₁) in the ¹³⁹La NQR signal was proportional to temperature (T) in zero external field above the superconducting transition temperature (T_c) or in an external field larger than the superconducting critical field, which means the system is in the Fermi-liquid state. In the superconducting state, on the other hand, 1/T₁ decreases no more linearly with T, but decreases rapidly exponentially as exp (−Δ/k_BT) at low T with an appreciable enhancement just below T_c. The value of the superconducting energy gap, 2Δ, was estimated to be 3.34k_BT_c, compared with 3.52k_BT_c of the BCS-value. This result strongly suggests that the superconductivity in LaNiC₂ is of a conventional BCS type.     

29Si and 19F MAS NMR spectra of isolated 29Si(19F)2 and 29Si(19F)3 spin systems: experiments and simulations

We consider ²⁹Si and ¹⁹F MAS NMR spectra of isolated ²⁹Si(¹⁹F)₂ and ²⁹Si(¹⁹F)₃ spin systems in two organosilicon compounds of the type RR’SiF₂ and RSiF₃(R,R′=organic ligands). Experimental spectra are analysed by means of numerical simulations. It is found that the SiF₃ group in RSiF₃ is reorienting rapidly around the molecular Si–C bond direction in the solid state. The two ¹⁹F shielding tensors in RR’SiF₂ have strongly differing orientations relative to the two Si–F bond directions in the molecule. Possibilities and limitations of straightforward MAS NMR approaches for the full characterisation of ²⁹Si(¹⁹F)₂ and ²⁹Si(¹⁹F)₃ spin systems and other dipolar coupled two and three-spin systems are discussed.     

27Al NMR study in ZrNiAl

We have studied the microscopic properties of the hexagonal ZrNiAl, a model compound for a wide family of intermetallic compounds crystallizing in this type of structure, by using ²⁷Al NMR spectroscopy. We have investigated the lineshape of static and MAS NMR spectra as a function of magnetic field strength (4.7–9.4 T) and temperature (5–300 K). Our data indicate that the ²⁷Al NMR spectra result from a combined effect of quadrupole and anisotropic shift interactions. The ²⁷Al nuclei are in an environment characterized by the quadrupole coupling constant e²qQ/h of 3.3 MHz, asymmetry parameter η_Q of 0.42, isotropic shift δ_iso of 393 ppm, shift anisotropy δ_anis = δ_zz − (δ_xx + δ_yy)/2 of 150 ppm, and asymmetry factor η_S of 0.5. They are found to be temperature independent. The spin–lattice relaxation rate measured at 7.05 T is proportional to the temperature with T₁T = 135 s K. The mechanisms responsible for observed values of δ_iso, δ_anis, T₁T, and the enhanced Korringa constant are discussed.     

Determination of titanium NMR parameters of ATiO3 compounds: correlations with structural distortion

Solid state ^47,49Ti NMR spectra have been obtained for a number of perovskite and ilmenite ATiO₃ compounds. The ⁴⁹Ti quadrupole coupling constant varies from 2.75 MHz (CaTiO₃) to 15.5 MHz (MgTiO₃) and the electric field gradient at the titanium site was found to correlate well with the shear strain, independent of structure. The chemical shift in the perovskite structures varies by 160 ppm and correlates well with the mean Ti–O distance. The ²⁵Mg and ¹¹³Cd NMR parameters are also reported for the relevant compounds.     

Neutron production in extended Cu-target irradiated with relativistic C-ions at Dubna, as studied with SSNTD and nuclear chemistry

An extended Cu-target was irradiated with 22 and 44 GeV carbon ions. The target was in contact with a (CH₂)_n-block for the moderation of secondary neutrons. Small holes in the moderator were filled with either lanthanium salts or uranium oxide. The reaction ¹³⁹La (n,γ) ¹⁴⁰La was studied via the decay of ¹⁴⁰La (40 h), and the reaction ²³⁸U (n, γ) ²³⁹U ²³⁹Np was studied via the decay of ²³⁹Np (2.3 d). In addition, a variety of solid state nuclear track detectors (SSNTD) were used. Results will be presented. The yields for the formation of (n, γ) products agree essentially with other experiments on extended targets carried out at the Synchrophasotron LHE, JINR (Dubna). To a first approximation, the breeding rate of (n, γ) products, as well as the specific track density, seen with several SSNTDs, doubles when the carbon energy is increased from 22 to 44 GeV. If, however, results at 44 GeV are compared in detail to those at 22 GeV, we observe an excess of (37 ± 9) % in the experimentally observed ²³⁹Np-breeding rate over theoretical estimations. Experiments using solid state nuclear track detectors are giving similar results. We also observed in the past such excess in the yield of other secondary particles in relativistic heavy ion interactions above a total energy of approximately 35–40 GeV.     

不同壳层厚度的LaF3：Eu3+/LaF3核壳结构纳米颗粒制备及发光性质

表面缺陷会使纳米材料的发光中心产生严重的猝灭，而适当厚度的同质包覆层会减少其猝灭。本文利用共沉淀法合成了LaF₃：Eu³⁺纳米颗粒和LaF₃：Eu³⁺/LaF₃核壳结构纳米颗粒，研究了颗粒的晶体结构、形貌以及不同壳层厚度对发光性能的影响。研究发现：LaF₃：Eu³⁺核心和LaF₃：Eu³⁺/LaF₃核壳结构均为六方结构。包覆同质壳层可以提高稀土离子的发光性能，包覆厚度的不同导致LaF₃：Eu³⁺/LaF₃核壳结构的荧光强度与衰减时间均发生改变。其原因是未掺杂的LaF₃壳层可以将发光中心Eu³⁺离子与LaF₃：Eu³⁺核心的表面隔离，进而减少表面对发光中心的猝灭，提高材料的发光性能。这种修饰作用与壳层厚度相关。     

FPT-CNDO/INDO化学屏蔽常数计算方法及其在Mo和Co化合物中的应用

Semi -empirical molecular orbital methods within the framework of the finite perturbation theory , the FPT-CNDO/INDO methods , which consist of the FPT-CNDO/2 and FPT-INDO methods, are set up for the study of chemical shielding in transition metal compounds, and a corresponding computational program is developed on VAX 11/785 computer to establish a theoretical study of the transition metal chemical shielding by quantum chemistry methods. Application of the methods has been carried out in the calculation of 95Mo chemical shielding constants of mononuclear precursors [MoOnS4-n]2-(n=0-4). With the standard CNDO/INDO parameters a linear regression was obtained between the calculated results and the corresponding experimental data:δcal=(0.8345 δexp-43.83)ppm, with a correlation coefficient of 0.999. Investigation on the calculated electronic configuration confirms that in [MoOnS4_n]2- (n=0-4)95Mo chemical shifts are dominated by the d-orbital paramagnetic contribution arising from the d-d transition. Appl     

High-field 127I NMR of solid sheelite structures: periodates revisited

We report new solid-state ¹²⁷I NMR results for sheelite periodates, MIO₄ (M = Na⁺ , K⁺ , Rb⁺ , and NH⁺ ₄), and for pseudo-scheelite CsIO₄ and HIO₄. The observed ¹²⁷I quadrupole coupling constants were between 1.0 and 43.0 MHz in agreement with previous NQR data. In contrast to an early ¹²⁷I NMR study (S. L. Segel and H. M. Vyas, 1980, J. Chem. Phys.72, 1406), we found that the ¹²⁷I chemical shift anisotropy is negligibly small in sheelite periodates. A small but definite ¹²⁷I chemical shift tensor was observed for pseudo-scheelite CsIO₄.     

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).     

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.     

Unusual observation of nitrogen chemical shift anisotropies in tetraalkylammonium halides by 14N MAS NMR spectroscopy

¹⁴N Magic-angle spinning (MAS) NMR spectra for a number of polycrystalline, symmetrical tetraalkylammonium halides with short alkyl chains (C₂H₅– to n-C₄H₉–) have been recorded following a careful setup of the experimental conditions. Analysis of the spectra demonstrates the presence of ¹⁴N chemical shift anisotropies (CSAs) on the order of |δ_σ|=10–30 ppm along with ¹⁴N quadrupole coupling constants in the range of 10–70 kHz. The magnitude and sign of the CSAs determined from ¹⁴N MAS NMR are confirmed by recording and analysis of the corresponding slow-speed spinning (500–650 Hz) ¹⁵N CP/MAS NMR spectra. Most interestingly, it is observed experimentally and demonstrated theoretically and by simulations, that these CSAs are reflected in the spinning sideband (ssb) intensities of the ¹⁴N MAS spectra at much higher spinning speeds than can be applied to retrieve the corresponding ¹⁵N CSAs from the ssb pattern in the ¹⁵N CP/MAS spectra.     

27Al NMR study in UNiAl

The ternary compound UNiAl exhibiting an antiferromagnetic order below T_N = 19.3 K has been studied in the paramagnetic state using the ²⁷Al NMR technique and different magnetically oriented samples. The quadrupole coupling constant e²qQ/h = 1.56 MHz is temperature independent. The dominant, longitudinal component of the Knight shift with respect to the hexagonal c axis, K, is positive and increases upon lowering the temperature down to 50 K. Much smaller in magnitude, the transverse component, K_±, is also positive and only slightly temperature dependent. The plots of the Knight shift vs magnetic susceptibility K(χ) and K_±(χ_±) form the same line, which implies that the transferred hyperfine field of 9.2 kOe/μB for ²⁷Al nuclei should be considered isotropic.     

Yb3+/Er3+共掺(MLaFn)x(M=0,K;n=3,4;x=1,1.5)纳米材料的控制合成及其上转换发光性质

采用水热与溶剂热结合的方法,在乙二醇-正己醇体系中,通过调节KF与RE(RE=La,Yb,Er)的量比、反应温度和反应时间实现了由LaF_3(六角相)到KLaF_4(立方相、六角相)晶型的控制合成。借助透射电子显微镜(TEM)和X射线粉末衍射(XRD)对样品的结构和微观形貌进行表征。结果表明,当KF/RE比例为2. 25时,制备的样品为片状的六角相LaF_3纳米颗粒;当KF/RE比例为3. 00时,得到具有近似球形的立方相KLaF_4纳米颗粒;当KF/RE比例为4. 25时,得到了六角相(KLaF_4)_(1. 5)纳米颗粒。上转换发射光谱显示:所有的样品在近红外光(980 nm)激发下,均有3个明显的发射峰,在522 nm、544 nm处分别对应于Er~(3+)的~4S_(3/2),~2H_(11/2)→~4I_(15/2)能级跃迁,655 nm处属于Er~(3+)的~4F_(9/2)→~4I_(15/2)能级跃迁。     

三环已基羧酸锡的13C和119Sn NMR研究

测定了33个三环己基脂肪族和芳香族羧酸锡在非配位溶剂(CDCl₃)中的¹³C和¹¹⁹Sn NMR谱。结果表明:化学位移δ(¹¹⁹Sn)值主要由锡原子的配位数决定,结构上微小的变化。都能在δ(¹¹⁹Sn)值上明显地表现出来。讨论了不同类型化合物间NMR参数间的关系。     

Preservation of endometallofullerene La@C82 in polycarbonate: EPR, ENDOR, and NMR studies

On embedding in poly(bisphenol A carbonate) film, La@C₈₂ has featured the exclusive stability against oxygen for more than 1 year's storage of the polymer films on air. The EPR spectral parameters of La@C₈₂ have occurred to be sensitive to the segmental mobility and the phase transition of the polymer from the glassy to the high-elasticity state. Furthermore, the intense matrix ¹H-electron nuclear double resonance (ENDOR) signal discovered in this system testifies the partial transfer of the electron spin density outside the fullerene cage onto the polymer protons. The ¹³⁹La NMR spectrum of the same suggests that La@C₈₂ forms nanoparticles, in which the metal atoms strongly interact with the delocalized electrons. The “spin-leakage” of the fullerene shell, along with the tendency of endohedral fullerenes (EMF) to form nanoparticles, is worth consideration in sight of their applications in material sciences.