不同耦合构型多自旋体系单重态制备效率研究

核自旋单重态是一种特殊的量子态,其存在寿命能远长于纵向弛豫时间(T₁),能够被用于研究分子之间的慢扩散和慢运动等动力学过程．单重态的制备是其能成功应用的关键．目前文献中报道了多种制备单重态的方法,这些方法主要适用于孤立的两自旋体系,当单重态所涉及的核自旋受到其它自旋的耦合作用时,单重态的制备效率往往会降低．本文以三自旋体系为例,研究了不同耦合构型下单重态的制备效率受非单重态自旋耦合的影响,模拟结果表明当单重态自旋由弱耦合逐渐变为强耦合时,单重态的制备效率会在单重态自旋与非单重态自旋的耦合呈现对称性时保持一定的稳定性,此特性能够为复杂体系中选择合适的自旋制备单重态提供参考．我们利用N-乙酰-L-天门冬氨酸(NAA)分子的三个质子组成的自旋体系实验验证了以上结论,通过调节NAA分子的酸碱度,所选的三自旋体系能从弱耦合向强耦合转变,实验结果表明：当三自旋中单重态自旋处于强耦合时,单重态的制备效率明显高于弱耦合时的效率．     

三自旋体系长寿命核自旋单重态的制备

长寿命核自旋单重态的寿命（T_S）可以长于常规的纵向弛豫时间（T₁）,基于这个独特的优势,长寿命核自旋单重态具有较好的应用价值.本文对已有脉冲序列进行了改进,给出了适用于任意三自旋弱耦合体系长寿命核自旋单重态制备的参数计算方法,发现在同一个三自旋体系内核自旋单重态具有多种不同比例系数组合的形式,并以丙烯酸为例制备出了两种长寿命核自旋单重态,实验上观察到不同的核自旋单重态的寿命存在差异,另外我们还探究了温度对丙烯酸核自旋单重态寿命的影响.     

三种脉冲序列制备核自旋单重态效率的比较

核自旋单重态的制备和检测在化合物分子的相关分析中具有重要的应用价值和广阔的应用前景.本文以三肽分子AGG（Ala-Gly-Gly）中两个质子构成的一组孤立的自旋耦合体系为研究对象,利用三组基于不同原理的脉冲序列,分别对该体系制备了核自旋单重态;并分别测定和比较了三种方法制备核自旋单重态的效率及其寿命.研究结果表明,对于同一分子的同一自旋耦合体系中的质子,使用不同的脉冲序列制备得到的核自旋单重态的寿命并不会有明显差异,但基于不同脉冲制备核自旋单重态的效率差异相对较大.     

用于指导仲氢诱导核极化状态保存的己烯分子中五自旋的单重态制备和寿命研究

仲氢诱导核极化（PHIP）技术能极大地增强核磁共振（NMR）信号的灵敏度,已被应用于磁共振成像、原位化学反应监测等领域．除了不断提高不同分子极化后的灵敏度外,延长和保存高极化度状态对PHIP技术的应用也至关重要,其中将极化后的状态制备成核自旋单重态是目前被研究较多的一种方法．本文以能被PHIP技术极化的己烯分子为研究对象,通过设计优化控制脉冲,对分子中的一个五自旋体系进行操控,制备了多种核自旋单重态,结果表明：己烯分子的碳-碳双键上存在三种不同的核自旋单重态,它们的寿命均长于仲氢极化后产生的初始态的寿命,可以作为延缓极化度衰减的一种中间态;通过对比单重态的寿命与相应自旋的纵向弛豫时间发现,将极化后己烯的状态转化为纵向磁化可能也是一种保存极化度的有效方法．     

核自旋单重态的制备及其转化效率和寿命的影响因素分析

长寿命核自旋单重态（LLS）因具有寿命较长这一特性而具有广泛的应用前景.本文在一个三肽样品（alanylglycylgcine，AGG）的水溶液中，对结构中离手性碳较远的二自旋体系进行核自旋单重态的制备，并探究了样品浓度、温度、射频发射中心位置、自旋体系之间的J耦合常数，以及磁场不均匀性五个因素对LLS的转化效率及其寿命的影响.实验结果表明，核自旋单重态的转化效率和寿命均不受样品浓度以及磁场不均匀性的影响.寿命会随实验温度的升高不断增加，转化效率随温度的下降而减小.射频中心位置在小范围内变化时，核自旋单重态制备所受影响不明显；但当变化较大时，其转化效率与寿命明显减小.同时，核自旋单重态对J耦合的变化则比较敏感，当J值选择不精准时，转化效率及寿命都出现明显降低.     

用SAC-CI方法研究Si(CH3)2O双自由基的基态、激发态、阳离子态和阴离子态

采用Nakatsuji提出的对称匹配耦合簇相互作用(SAC-CI)方法,计算了Si(CH3)2O双自由基分子的基态,单重三重激发态,阳离子二重态和阴离子二重态的激发能,光电子谱,电离能等.结果表明,SAC-CI方法比TDDFT有明显优势.     

表面单分子量子态的探测和调控研究进展

单分子体系是一种典型的受限量子体系,且由于其能级分立、轨道局域、化学拓展性强,因而具有丰富的电子态、光子态以及自旋态,这些分子体系中由量子力学决定的物态使得利用单分子作为未来量子信息的载体成为可能.对单分子尺度量子态的探测和调控研究有利于我们“自下而上”精确构建量子器件.由于单分子体系的尺寸限制,宏观的表征手段难以对其进行精确地调控和探测.扫描隧道显微镜具有高精度的实空间定位能力,高分辨的成像和谱学能力,可以实施原位的分子操纵,还可以与多种外场和局域场表征技术联用,是目前精确探测和调控分子尺度量子态特性的重要工具.本文撷取这一领域较为代表性的进展,介绍了基于扫描隧道显微学技术的表面吸附单分子及其相关结构中的量子态研究现状.首先介绍了表面单分子体系量子态的制备手段,然后分别重点介绍了单分子的局域磁自旋态以及单分子作为单光子源的光学特性.对于石墨烯分子结构我们将其视为一种大分子的单分子体系,分别从其拓扑电子态和自旋态的表征和调控两方面做了介绍.最后总结并对单分子量子态研究未来的发展做了展望.     

143 Pm高自旋态研究

通过熔合蒸发反应128Te(19F,4nγ)布居了143Pm的高自旋态,利用在束γ谱学方法,对143Pm的高自旋态核结构进行了研究.测量了γ射线单谱和γ-γ符合谱,并进行了γ射线各向异性以及DCO比率分析,建立了激发能高达10535.4keV的能级纲图,其中包括新发现的32条γ射线和17个新能级.用弱耦合模型对143Pm的晕态能级结构进行了解释.     

^143Pm高自旋态研究

通过熔合蒸发反应^129Te(^19F,4nγ）布居了^143Pm的高自旋态,利用在束γ谱学方法,对^143Pm的高自旋态核结构进行了研究,测量了γ射线单谱和γ－γ符合谱,并进行了γ射线各向异性以及DCO比率分析,建立了激发高能达10535．4keV的能级纲图,其中包括新发现的32条γ射线和17个新能级,用弱耦合模型对^143Pm的晕态能级结构进行了解释。     

BaCrSi4O10与AgGaSe2:Cr2+吸收光谱的精细结构及自旋单态对零场分裂参量的影响

在强场图像中构造了四角对称环境中Cr²⁺离子包括自旋单态在内的完全能量矩阵, 通过对角化能量矩阵方法, 计算得到了BaCrSi₄O₁₀与AgGaSe₂:Cr²⁺吸收光谱的精细结构及自旋单态对零场分裂参量的影响. 从理论上给出了BaCrSi₄O₁₀与AgGaSe₂:Cr²⁺吸收光谱的精细结构及BaCrSi₄O₁₀的零场分裂参量值. 计算结果显示自旋单态对零场分裂参量D的影响完全可忽略, 但对a和F的影响比较大. 这种影响主要来自自旋-轨道耦合导致的自旋五重态与自旋三重态和自旋单态的相互作用, 而自旋轨道耦合的选择定则显示自旋单态并非直接影响五重态而是通过自旋三重态间接地影响基态的五重态. 因此, 为了得到准确的零场分裂参量值, 所有的自旋态都应该考虑.     

液体核磁共振 HSQC 实验的量子化学计算与模拟

核磁共振（NMR）异核单量子相干（HSQC）实验因具有较高的灵敏度和分辨率而被广泛用于液体大分子化合物的结构鉴定和研究．然而由于HSQC脉冲的复杂性,需要严格控制实验参数和实验条件才能得到高质量的谱图．本文基于量子力学原理对HSQC实验进行数学建模,通过理论推导、数值计算求解自旋1/2的IS双核体系在每个脉冲节点作用后的密度矩阵,然后结合二维NMR信号采样方法,使用计算机程序完成了该体系HSQC谱图的模拟,同时,还实现了乙醇分子的HSQC谱图模拟． HSQC实验的成功模拟基于对复杂演化过程的精确计算,可用于预测谱图以及实验参数改变对NMR谱图的影响,指导高质量HSQC实验谱图的采集．     

Incorporating homonuclear polarization transfer into PRESS for proton spectral editing: illustration with lactate and glutathione

A proton spectral editing pulse sequence for the detection of metabolites with spin systems that involve weak coupling is presented. The sequence is based on homonuclear polarization transfer incorporated into the standard PRESS (Point RESolved Spectroscopy) sequence, which is a volume-selective double spin echo method, to enable spatial localization. All peaks in the region of interest are initially suppressed whether they are peaks from the target metabolite or from contaminating background. The target signal is then restored by polarization transfer from a proton that has a resonance outside the suppressed region and to which the target spins are weakly coupled. This is achieved by the application of a 90 degrees hard pulse with phase orthogonal to that of the PRESS excitation pulse at the location of the first echo in PRESS and by optimizing the two PRESS timings, TE(1) and TE(2), for most efficient yield. Background signal not coupled to any protons outside the initially saturated region remains suppressed. The advantage of this sequence compared to multiple quantum filters is that signal from singlet peaks outside the suppressed area are preserved and can thus be used as a reference. The efficacy of the sequence was verified experimentally on phantom solutions of lactate and glutathione at 3.0 T. For the AX(3) spin system of lactate, the sequence timings were optimized by product operator calculations whereas for the ABX spin system of the cysteinyl group of glutathione numerical calculations were performed for sequence timing optimization.     

多量子比特核磁共振体系的实验操控技术

随着量子信息与量子计算科学的发展,量子信息处理器被广泛地用于量子计算、量子模拟、量子度量等方面的研究.为了能在实验上实现这些日益复杂的方案,将量子计算机的潜能转化成现实,需要不断提高可操控的量子体系比特位数,实现更复杂的量子操控.核磁共振自旋体系作为一个优秀的量子实验测试平台,提供了丰富而又精密的量子操控手段.近几年来在此平台上进行了不少的多量子比特实验,发展并积累了一系列的多量子比特实验技术.本文首先阐述了核磁共振体系多量子比特实验中的实验困难,然后结合7量子比特标记赝纯态制备以及其他有关实验,对多比特实验过程中应用到的实验技术进行介绍.最后对核磁共振体系多量子比特实验技术方向的进一步研究进行了总结和展望.     

A New Two-Dimensional Pulse Sequence for T2* Measurements of Protons in C Isotopomers

A new two-dimensional pulse sequence for T₂* measurement of protons directly coupled to ¹³C spins is proposed. The sequence measures the tranverse relaxation time of heteronuclear proton single-quantum coherence under conditions of free precession and is therefore well suited to evaluate relaxation losses of proton magnetization during preparation delays of heteronuclear pulse experiments in analytical NMR. The relevant part of the pulse sequence can be inserted as a “building block” into any direct or inverse detecting H,C correlation pulse sequence if proton spin–spin relaxation is to be investigated. In this contribution, the building block is inserted into a HETCOR as well as into a HMQC pulse sequence. Experimental results for the HETCOR-based sequence are given.     

<Emphasis Type="Italic">cis</Emphasis> Versus <Emphasis Type="Italic">trans</Emphasis>-Azobenzene: Precise Determination of NMR Parameters and Analysis of Long-Lived States of <Superscript>15</Superscript>N Spin Pairs

We provide a detailed evaluation of nuclear magnetic resonance (NMR) parameters of the cis- and trans-isomers of azobenzene (AB). For determining the NMR parameters, such as proton–proton and proton–nitrogen J-couplings and chemical shifts, we compared NMR spectra of three different isotopomers of AB: the doubly ¹⁵N labeled azobenzene, ¹⁵N,¹⁵N′-AB, and two partially deuterated AB isotopomers with a single ¹⁵N atom. For the total lineshape analysis of NMR spectra, we used the recently developed ANATOLIA software package. The determined NMR parameters allowed us to optimize experiments for investigating singlet long-lived spin states (LLSs) of ¹⁵N spin pairs and to measure LLS lifetimes in cis-AB and trans-AB. Magnetization-to-singlet-to-magnetization conversion has been performed using the SLIC and APSOC techniques, providing a degree of conversion up to 17 and 24% of the initial magnetization, respectively. Our approach is useful for optimizing the performance of experiments with singlet LLSs; such LLSs can be exploited for preserving spin hyperpolarization, for probing slow molecular dynamics, slow chemical processes and also slow transport processes.     

Preparing high purity initial states for nuclear magnetic resonance quantum computing

Here we demonstrate how parahydrogen can be used to prepare a two-spin system in an almost pure state which is suitable for implementing nuclear magnetic resonance quantum computation. A 12 ns laser pulse is used to initiate a chemical reaction involving pure parahydrogen (the nuclear spin singlet of H2). The product, formed on the micros time scale, contains a hydrogen-derived two-spin system with an effective spin-state purity of 0.916. To achieve a comparable result by direct cooling would require an unmanageable (in the liquid state) temperature of 6.4 mK or an impractical magnetic field of 0.45 MT at room temperature. The resulting spin state has an entanglement of formation of 0.822 and cannot be described by local hidden variable models.     

Selective polarization inversion of protons in rotating solids

The selective inversion of lines under phase modulated Lee-Goldburg (PMLG) decoupling in MAS proton spectroscopy is demonstrated. Short pulses inserted between consecutive PMLG irradiation intervals selectively invert the polarization of an on-resonance line while sustaining a high resolution proton evolution. The pulse scheme is combined with windowed-PMLG detection to obtain a one-dimensional high resolution spectrum with one of the proton lines inverted. Initial preparation of the protons in selectively inverted states can be used to follow the flow of polarization during spin diffusion. Examples of proton-proton spin exchange in alanine and histidine are demonstrated. Selective inversion is also used in conjunction with proton carbon LG-cross-polarization to achieve carbon spectra with lines characterized by different polarization states.