锗酸铋(Bi4Ge3O12)中铋(209Bi)核的零场核磁共振研究

锗酸铋(Bi₄Ge₃O₁₂)作为一种新型的有发展前景的单晶闪烁材料,使得对这种材料的各种性质的研究很能引起人们的兴趣。本工作的目的是想通过核磁共振这一方法对锗酸铋样品的研究,得到有关其微观结构方面有用的信息。尝试性实验的结果说明锗酸铋中铋核具有非常强的四极相互作用,在7.0T的磁场下,铋核的核磁共振谱成为一个无法测量的宽谱。本文利用了零场这个实验条件,成功地避开了强四极耦合引起的在磁场下的谱线变宽的困难,在Bncker-MSL300脉冲FT核磁共振谱仪上首次精确地测定了国产锗酸铋单晶粉末样品中²⁰⁹Bi核的四极耦合常数:高温下e²qθ/h=1474.18MHz。我们还在288K到150K的温度范围内测量了四极耦合常数的温度效应。发现在这个温度区域²qθ/h的值在1509.59MHz至1474.00MHz之间有规律的变化。极强的四极相互作用和明显的温度效应可能暗示着某种有待进一步研究的现象的存在。D.Brinkmann和A.B.Dension在一九七二年为研究电光晶体(electro-optic crystal)的性质,用单晶核磁共振的方法得到e²qθ/h的值为488±1MHz的结果^[1],与本实验得到的值相差很大。这种差別的原因也有待进一步研究。     

化学位移各向导性对半整数自旋四极核的2D NMR章动的影响

考察了化学位移各向异性对半整数自旋四极核2D NMR章动的影响.用数值方法对2D NMR章动实验的演化期的Hamiltonian矩阵进行对角化,然后用帐篷法进行粉末平均,获得了自旋为I=3/2、5/2、7/2和9/2的四极核在不同化学位移各向异性下的2D NMR章动谱.实验结果与理论计算符合较好.     

场效应管核电四极共振谱仪

本文描述了一台场效应管超再生核四极共振谱仪的工作原理和性能;谱仪的振荡检波级是作者研制的一个频率覆盖范围较宽、灵敏度较高的场效应管(FET)超再生振荡检波器。文中还给出用本谱仪显示、记录的部分化学样品中的³⁵Cl核和³⁷Cl核的核四极共振(NQR)谱,并对使用场效应管的超再生振荡检波器的灵敏度作初步探讨。     

嵌段共聚物溶致液晶相中水的2H-NMR动力学分析

采用D₂O 的²H-NMR线型和弛豫分析了PEO-PPO-PEO/D₂O/对二甲苯体系的层状和六角液晶相的动力学行为. 通过实验测得了两个不同体系的自旋 晶格弛豫时间T₁、自旋-自旋弛豫时间T₂和²H-NMR 谱. ²H-NMR 谱均为具有四极劈裂的粉末谱线型，且在谱图的中心，β_LD=54.7°时存在一个倒峰. 倒峰的出现直接表明引起体系中弛豫的主要动力学过程处于极窄化区域. 采用NMR弛豫模型，通过调节动力学参数，使理论模拟的²H-NMR谱、弛豫时间、倒峰的大小与实验的对应量相吻合，求得了体系的动力学参数.     

化学位移各向导性对半整数自旋四极核的2D NMR章动的影响(英文)

考察了化学位移各向异性对半整数自旋四极核2DNMR章动的影响．用数值方法对2DNMR章动实验的演化期的Hamiltonian矩阵进行对角化，然后用帐篷法进行粉末平均，获得了自旋为I＝3／2、5／2、7／2和9／2的四极核在不同化学位移各向异性下的2DNMR章动谱．实验结果与理论计算符合较好．     

14N核四极共振自旋系统自旋-晶格弛豫时间的测量

¹⁴N核四极共振自旋系统的自旋-晶格弛豫是一种双指数弛豫。本文介绍了¹⁴N核四极共振自旋系统的自旋-晶格弛豫时间的3种测量方法,利用可变多面体方法对实验数据进行拟合,获得了¹⁴N核四极共振自旋系统的自旋-晶格弛豫时间T_1s和T₁₁,对有关文献中关于核四极共振弛豫时间的测量的3个观点提出了质疑。     

粉末样品自旋3/2四极核中心跃迁的高分辨核磁共振谱

本文利用脉冲对自旋3/2四极核中心跃迁激发的选择性,在粉末样品中用一个90°脉冲将电场梯度张量在空间某一取向的核自旋磁化矢量转到旋转坐标系中XY平面进行检测,从而得到与单晶样品类似的高分辨谱线,在理论上用密度算符公式作了分析,实验上用NaNO₂和Na₂SO₄粉末样品进行了验证。 关键词：     

旋转样品核四极共振的量子绝热微扰论分析

结合验证Berry几何相因子的Tycko旋转样品核四极共振实验,针对简并情况进一步发展并完善了作者之一最近提出的量子绝热微扰理论.应用这个理论,详细分析了任意自旋情况下具有核四极矩的旋转样品在射频场中的共振吸收,指出了可能的新的实验现象. 关键词：     

SnO2 ∶ Eu3+ 纳米晶的水热法制备及发光性能

采用水热法制备了Eu³⁺掺杂SnO₂纳米发光粉,样品在不同温度下热处理得到不同粒径尺寸的纳米颗粒。利用X射线衍射(XRD)与光致发光(PL)谱对样品进行表征。XRD分析表明:SnO₂ ∶ Eu³⁺样品均为纯相 金红石结构。PL测量表明:水热法直接制备的样品的激发谱由Eu³⁺的f-f本征激发峰组成,而经过热处理后样品的激发谱由O^2--Eu³⁺电荷迁移带和Eu³⁺的f-f本征激发组成;样品的发光强度与颗粒大小有密切关系。     

自旋I=3/2核四极共振体系对梳状脉冲的响应

用密度矩阵理论和计算机模拟较详细地讨论了自旋I=3/2核四极共振(NQR)粉末体系对梳状脉冲的响应以及偏共振效应的影响.在偏共振强度(包括谱线的非均匀增宽)较小的条件下.由它获得的谱与二维章动谱是相似的.但是实验所需时间能够减少近两个数量级. 关键词：     

Rotor-encoded heteronuclear MQ MAS NMR spectroscopy of half-integer quadrupolar and spin I=1/2 nuclei

A new two-dimensional heteronuclear multiple-quantum magic-angle spinning (MQ MAS) experiment is presented which combines high resolution for the half-integer quadrupolar nucleus with information about the dipolar coupling between the quadrupolar nucleus and a spin I=1/2 nucleus. Homonuclear MQ coherence is initially created for the half-integer quadrupolar nucleus by a single pulse as in a standard MQ MAS experiment. REDOR recoupling of the heteronuclear dipolar coupling then allows the creation of a heteronuclear multiple-quantum coherence comprising multiple- and single-quantum coherence of the quadrupolar and spin I=1/2 nucleus, respectively, which evolves during t1. Provided that the t1 increment is not rotor synchronized, rotor-encoded spinning-sideband patterns are observed in the indirect dimension. Simulated spectra for an isolated IS spin pair show that these patterns depend on the recoupling time, the magnitude of the dipolar coupling, the quadrupolar parameters, as well as the relative orientation of the quadrupolar and dipolar principal axes systems. Spectra are presented for Na2HPO4, with the heteronuclear 23Na-1HMQ MAS experiments beginning with the excitation of 23Na (spin I=3/2) three-quantum coherence. Coherence counting experiments demonstrate that four- and two-quantum coherences evolve during t1. The heteronuclear spinning-sideband patterns observed for the three-spin H-Na-H system associated with the Na(2) site are analyzed. For an IS2 system, simulated spectra show that, considering the free parameters, the spinning-sideband patterns are particularly sensitive to only, first, the angle between the two IS internuclear vectors and, second, the two heteronuclear dipolar couplings. It is demonstrated that the proton localization around the Na(2) site according to the literature crystal structure of Na2HPO4 is erroneous. Instead, the experimental data is consistent with two alternative different structural arrangements, whereby either there is a deviation of 10 degrees from linearity for the case of two identical Na-H distances, or there is a linear arrangement, but the two Na-H distances are different. Furthermore, the question of the origin of spinning-sidebands in the (homonuclear) MQ MAS experiment is revisited. It is shown that the asymmetric experimental MQ sideband pattern observed for the low-C(Q) Na(2) site in Na(2)HPO4 can only be explained by considering the 23Na chemical shift anisotropy.     

Application of the Floquet theory to multiple quantum NMR of dipolar-coupled multi-spin systems under magic angle spinning

A new analytical Liouville-space representation of the time-propagator under magic angle spinning (MAS) is introduced using the formalized quantum Floquet theory. This approach has the advantage that it is applicable to the analysis of any type of NMR experiment where MAS is combined with multiple-pulse excitation. General relationships describing the spectral parameters in multiple-quantum (MQ) MAS spectra are derived in this representation. Their use is illustrated with an application to double-quantum (DQ) NMR spectra of dipolar-coupled multi-spin systems. Corresponding to the separation of the MAS time-propagator into a rotor modulated and a dephasing component, two distinct mechanisms for DQ excitation are identified. One of them exploits the rotor-modulated component to excite DQ coherences through dipolar-recoupling techniques, which are familiar for spin pairs. Analytical expressions of the integral intensities and linewidths in the resulting DQ sideband pattern are derived in the form of power series expansions of the inverse rotor frequency, of which coefficients depend on structural parameters. In a multi-spin system they can most reliably be extracted in the fast spinning regime. The other mechanism exploits the dephasing component, which is characteristic to multi-spin systems only. This is shown to give rise to DQ coherences by free evolution at full rotor periods. The possibility to exploit it for selective excitation of higher order MQ coherences is discussed. In either case, the dephasing component also leads to residual broadening. The main results of the theoretical developments are demonstrated experimentally on adamantane.     

High-resolution 1H NMR spectroscopy in the solid state: very fast sample rotation and multiple-quantum coherences

In the past few years, solid-state 1H NMR spectroscopy under fast magic-angle spinning (MAS) has developed into a versatile tool for elucidating structure and dynamics. Dipolar multiple-quantum (MQ), in particular double-quantum (DQ), MAS spectroscopy has been applied to a variety of materials and provided unique insight, e.g., into the structure of hydrogen-bonded systems. This review intends to present solid-state 1H DQ and MQ MAS spectroscopy in a systematic fashion with a particular emphasis on methodological aspects, followed by an overview of applications.     

High-Resolution H NMR Spectroscopy in the Solid State: Very Fast Sample Rotation and Multiple-Quantum Coherences

In the past few years, solid-state ¹H NMR spectroscopy under fast magic-angle spinning (MAS) has developed into a versatile tool for elucidating structure and dynamics. Dipolar multiple-quantum (MQ), in particular double-quantum (DQ), MAS spectroscopy has been applied to a variety of materials and provided unique insight, e.g., into the structure of hydrogen-bonded systems. This review intends to present solid-state ¹H DQ and MQ MAS spectroscopy in a systematic fashion with a particular emphasis on methodological aspects, followed by an overview of applications.     

魔角旋转核磁共振波谱学

样品绕与外加恒定磁场方向成魔角β_M=cos^-1(1)/√3的轴向快速旋转(MAS)可以消除固体NMR的多种谱增宽。本文首先介绍了固体中的几种主要的各向异性相互作用,即偶极-偶极,核四极,自旋-自旋或称间接偶极-偶极以及化学位移相互作用。然后用平均哈密顿理论阐述了MAS对这些相互作用的影响。现今的固体高分辨方法有四种,即多脉冲(MP),多量子(MQ),交叉极化和大功率异核去耦合(CP)以及MAS,在这些方法中MAS方法是唯一可以获得各向同性化学位移的。因而要得到类似于液体谱的固体高分辨,MAS往往是最后的手段。以上这些方法的联合运用以及极为广泛的应用研究使得固体高分辨NMR兴旺发达起来了。本文引述了大量原始和最新的文献,力图概述当前该领域中的大部分成就。评论这一领域的理论和实验技术的发展。     

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。     

Tb3+和Na2WO4共掺杂SiO2材料的制备及其发光性质

通过溶胶-凝胶技术制备了稀土离子Tb3 和Na2WO4共掺杂的SiO2材料,利用DTA-TG,IR,XRD等测试手段研究了材料的结构。材料属于非晶态,800℃退火后Tb3 和Na2WO4共掺杂样品的主要结构为SiO2的网状结构。通过三维荧光光谱,荧光激发光谱和发射光谱,分析探讨了Na2WO4对掺稀土离子的SiO2体系发光性质的影响。结果显示,在230nm激发下,样品显示Tb3 的5D4—7Fj(j=4,5,6)和5D3—7Fj(j=4,5,6)发射光谱,在紫外灯的照射下,发射均匀的蓝绿色荧光,说明样品掺杂均匀且分散性较好。Na2WO4的掺入,并不影响Tb3 在SiO2基质中的发射峰的主要位置,但对发光强度有很大的影响,敏化了5D4—7F6蓝色跃迁而猝灭了5D4—7F5绿色跃迁,使材料发射蓝绿色荧光。文章通过所得的能级图,对样品的跃迁机理进行了分析。     

Investigations of low-amplitude radio frequency pulses at and away from rotary resonance conditions for I = 5/2 nuclei

Additional experimental evidence of rotary resonance effects for multiple-quantum coherence conversion in a spin-5/2 system is presented. Two-dimensional plots of the relative efficiency of MQ excitation and conversion are given as a function of radio frequency (rf) amplitude and pulse width. Data are presented for the excitation of five-quantum coherence (5QC), as well as for 5QC to three-quantum coherence (3QC) conversion, 5QC to IQC (the central transition coherence) conversion, and 3QC to IQC conversion. A two-fold increase in the signal-to-noise ratio is achieved by substituting low amplitude rf pulses in place of hard rf pulses for 5QC excitation and 5QC to 3QC conversion in a mixed multiple-quantum magic angle spinning (MAS) (MMQMAS) experiment. The anisotropic line shape for the low-amplitude rf pulse version of the MMQMAS experiment was observed to be distorted from the MAS line shape. The cause and implications of the distortion are discussed.     

Dual processing of two-dimensional exchange data in magic angle spinning NMR of solids.

We discuss procedures for processing data in rotor-synchronized two-dimensional magic angle spinning (2D MAS) NMR exchange measurements for both structural and dynamical studies. We show, both mathematically and experimentally, that there are two distinct data processing procedures that lead to 2D MAS exchange spectra with purely absorptive crosspeaks. One procedure is that described previously by Hagemeyer, Schmidt-Rohr, and Spiess (HSS). The other procedure is related, but different, and leads to crosspeak intensities given by the formulae of Herzfeld, Roberts, and Griffin (HRG). In 2D MAS exchange experiments on doubly (13)C-labeled l-alanylglycylglycine, we demonstrate that the HSS and HRG crosspeak intensities can be extracted separately from the same data set and contain independent information. Processing and analysis of 2D MAS exchange data with both the HSS and the HRG procedures may enhance utilization of the information content of 2D MAS exchange measurements.     

A Solid-State NMR Investigation of MQ Silicone Copolymers

The structure of MQ copolymers of the general chemical formula [(CH₃)₃SiO_0.5]_m [SiO₂]_n was characterized by means of solid-state magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The MQ copolymers are highly branched polycyclic compounds (densely cross-linked nanosized networks). MQ copolymers were prepared by hydrolytic polycondensation in active medium. ²⁹Si NMR spectra were obtained by single pulse excitation (or direct polarization, DP) and cross-polarization (CP) ²⁹Si{¹H} techniques in concert with MAS. It was shown that material consist of monofunctional M (≡SiO Si (CH₃)₃) and two types of tetrafunctional Q units: Q⁴ ((≡SiO)₄ Si) and Q³ ((≡SiO)₃ SiOH). Spin–lattice relaxation times T ₁ measurements of ²⁹Si nuclei and analysis of ²⁹Si{¹H} variable contact time signal intensities allowed us to obtain quantitative data on the relative content of different sites in copolymers. These investigations indicate that MQ copolymers represent dense structure with core and shell.