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.     

Correlation between P chemical shift tensor and local structure in lithium cyclohexaphosphates Li6P6O18·3H2O and Li6P6O18

To understand the surprising behavior between the variations of the P′–P–P″ angles and the correlated variations of the O′–P–O″ ones, two lithium cyclohexaphosphate compounds Li₆P₆O₁₈·3H₂O and Li₆P₆O₁₈ are studied by solid state nuclear magnetic resonance (NMR) spectroscopy. The two compounds exhibit the same [P₆O₁₈]⁶⁻ ring anions but with 3m or internal symmetry, respectively. Such symmetries induce local distortions that are exhibited by NMR spectroscopy. One-dimensional (1D) NMR gives information on structural sites of ⁷Li and ³¹P ions and the crystallographic non-equivalencies are observed. Nevertheless, in the anhydrous compound, X-ray diffraction and NMR results do not completely agree and some discrepancy exists between the number of sites observed with the first technique and the number of lines exhibited in the NMR spectra either for ⁷Li or ³¹P nuclei. This problem is elucidated by using 2D double quantum NMR spectroscopy coupled with theoretical considerations. We find that the ³¹P chemical shift tensor is dependent on the deviations of the O–P–O angles from those in the regular tetrahedron. Within the same empirical model, we suggest that the surprising behavior between the variations of the P′–P–P″ and the ones of the O′–P–O″ is related to the overall charge on the PO₄ group. We also find the positions of the isotropic lines for ⁷Li essentially depend on the site co-ordination of this nuclei.     

Carbon-13 and Fluorine-19 NMR Spectroscopy of the Supramolecular Solid p-tert-Butylcalix[4]arene ·α,α,α-trifluorotoluene

The supramolecular 1 : 1 host–guest inclusion compound, p-tert-butylcalix[4]arene ·α,α,α-trifluorotoluene, 1, is characterized by ¹⁹F and ¹³C solid-state NMR spectroscopy. Whereas the ¹³C NMR spectra are easily interpreted in the context of earlier work on similar host–guest compounds, the ¹⁹F NMR spectra of solid 1 are, initially, more difficult to understand. The ¹⁹F{¹H} NMR spectrum obtained under cross-polarization and magic-angle spinning conditions shows a single isotropic resonance with a significant spinning sideband manifold. The static ¹⁹F{¹H} CP NMR spectrum consists of a powder pattern dominated by the contributions of the anisotropic chemical shift and the homonuclear dipolar interactions. The ¹⁹F MREV-8 experiment, which minimizes the ¹⁹F–¹⁹F dipolar contribution, helps to identify the chemical shift contribution as an axial lineshape. The full static ¹⁹F{¹H} CP NMR spectrum is analysed using subspectral analysis and subsequently simulated as a function of the ¹⁹F–¹⁹F internuclear distance (D_FF = 2.25 ± 0.01 Å) of the rapidly rotating CF₃ group without including contributions from additional libration motions and the anisotropy in the scalar tensor. The shielding span is found to be 56 ppm. The width of the centerband in the ¹⁹F{¹H} sample-spinning CP NMR spectrum is very sensitive to the angle between the rotor and the magnetic field. Compound 1 is thus an attractive standard for setting the magic angle for NMR probes containing a fluorine channel with a proton-decoupling facility.     

Harmonics-to-noise ratios in normally speaking prepubescent girls and boys

This study examined harmonics-to-noise ratios (HNR) in 4 groups of normally speaking children. HNRs were calculated for the vowels /ai/ and /inverted v/, selected from conversational speech samples of 80 children aged 4, 6, 8, and 10 years (10 boys and 10 girls at each age level). HNR values for /inverted v/ were significantly higher than those for /ai/. Significant age differences emerged for /ai/ between ages 4 and 8, and ages 8 and 10. Girls obtained significantly higher HNRs than boys for the /ai/ vowel. Overall, the HNR values for these normally speaking children were lower than those reported for normally speaking adults. These findings suggest that acoustic values for children cannot be validly compared to those for adults, and that the child's gender and age should be taken into account when applying spectral analyses to research and/or clinical situations.     

激光冷却铯原子喷泉频标的黑体辐射频移

研究了激光冷却铯原子喷泉频标的黑体辐射频移（包括黑体辐射塞曼频移和黑体辐射斯塔克频移）,推导了频移的计算公式,估算了室温下频移及其不确定度的大小,分析了黑体辐射频移对频标准确度的影响。结果表明：１）室温下黑体辐射塞曼频移可达１０＾－１５量级,在评定铯原子喷泉频标准确度时,需要对此项频移加以修正;２）在利用直流斯塔克效应估算黑体辐射斯塔克频移时,由直流极化率常数ｘ的测量误差导致的黑体辐射斯塔克频移的     

有机染料TMQ掺杂的SiO2薄膜的光谱特性

采用溶胶 -凝胶法合成了紫外波段有机染料 TMQ掺杂的 Si O2 薄膜和块体材料。薄膜中掺杂的染料浓度高达 1.2 4× 10 -2 mol/ L,块体材料中染料浓度可掺至 1.5× 10 -3 mol/ L。由于Si O2 “笼”的束缚作用 ,在吸收光谱中未观察到二聚体的特征谱带 ,在荧光光谱中未观察到荧光猝灭现象 ;同时由于 Si O2 “笼”的极化作用 ,其吸收峰和发射峰的位置相对于其在环己烷溶液中的吸收峰和发射峰位置发生了 10 nm左右的红移。     

铅测定中的二条谱线对比

本文介绍了对铅的二条灵敏谱线进行的实验对比,结果证明２１７．０ｎｍ谱线的灵敏度增加一倍以上,其他指标也接近２８３．３ｎｍ谱线,可以用于卫生检测。     

A Hidden Chaotic System with Multiple Attractors

This paper reports a hidden chaotic system without equilibrium point. The proposed system is studied by the software of MATLAB R2018 through several numerical methods, including Largest Lyapunov exponent, bifurcation diagram, phase diagram, Poincaré map, time-domain waveform, attractive basin and Spectral Entropy. Seven types of attractors are found through altering the system parameters and some interesting characteristics such as coexistence attractors, controllability of chaotic attractor, hyperchaotic behavior and transition behavior are observed. Particularly, the Spectral Entropy algorithm is used to analyze the system and based on the normalized values of Spectral Entropy, the state of the studied system can be identified. Furthermore, the system has been implemented physically to verify the realizability.     

Relativistic effects and the halogen dependencies in the 13C chemical shifts of CH4−nIn,CH4−nBrn,CCl4−nIn,and CBr4−nIn (n=0–4)

Linear and nonlinear halogen dependencies of the ¹³C magnetic shielding constants of CH_4−nI_n, CH_4−nBr_n, CCl_4−nI_n, and CBr_4−nI_n were fairly reproduced by the ab initio generalized unrestricted Hartree–Fock (GUHF)/finite perturbation (FP) method including spin‐orbit (SO) interaction and spin‐free relativistic (SFR) terms. As seen from the experimental trends, the calculated ¹³C chemical shifts in CCl_4−nI_n and CBr_4−nI_n depend linearly on n=0–4, while those in CH_4−nI_n and CH_4−nBr_n depend nonlinearly. We found that both the linear and nonlinear dependencies are due to the relativistic effects, and especially due to the Fermi–Contact (FC) term originating from the SO interaction. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 528–536, 2001