太赫兹辅助测量铷原子超快量子相干过程的理论研究

太赫兹辅助光电离瞬态测量方法可以分辨超快量子拍频,同时对复杂量子系统的超快密度矩阵演化进行成像.本文依据这种方法提出了一种具体的实验方案,利用紫外脉冲(脉宽为30 fs)和高强度太赫兹脉冲(峰值场强:约1 MV/cm)组成复合探测电场,探测铷原子5S1/2和5P3/2叠加态振荡周期约为2.6 fs的量子拍频过程,量子体系密度矩阵演化的布居项和相干项投影在光电子动量谱的不同位置,可以对密度矩阵演化实现完全信息测量.本文设计的实验方案不需要阿秒高次谐波或自由电子激光等复杂的先进光源,可以成为探索复杂量子体系超快相干动力学过程的新方案.     

凝聚相中电子相干态的二维电子光谱测量（英文）

可见光波段的傅里叶变换二维电子光谱可用于对凝聚相分子复杂动力学过程的直接测量,包括量子相干现象.本文在对二维电子光谱原理的理解和对其物理本质更为直觉描述间做了一些铺垫,起到普及二维电子光谱的作用.重点阐述了二维电子光谱在测量电子相干态过程中是如何克服来自于量子力学原理的两大限制,即不确定性原理和测量导致的波包坍缩,并最终实现以本征态能级差为量子拍频的相干态测量.重点讨论了纯电子态相干、电子态与单模振动态耦合的相干,以及电子态与多模振动耦合形成的相干态所导致的复杂的量子相干现象.最后简要讨论了区分电子态相干及电子态-振动态耦合相干态的最新实验进展.     

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：     

自旋置换对称体系多脉冲及二维核磁共振实验的密度算符描述(Ⅱ)——多量子积算符方法

在对称化乘积算符(简称SAPO)方法基础上提出了多量子积算符(简称MQCPO)方法。改进的密度算符理论对I_nS(I=1/2,S=1/2;n为任意正整数)自旋体系多脉冲及二维核磁共振实验的描述普遍适用。MQCPO与SAPO从不同角度反映了自旋体系的对称性,故它们之间存在简单线性关系。文中给出I_n(I=1/2,n=2,3)自旋体系MQCPO的SAPO表示。MQCPO有利于自由演化过程的描述,而脉冲作用的描述则是SAPO为佳;利用MQCPO与SAPO的线性关系及SAPO笛卡儿分量的坐标轮换性质,“z”表象下脉冲作用的描述变得简单而直观。对异核谱剪辑及自旋拓扑滤波(spin topology filtration)等实验脉冲序列的分析,该方法是方便的。 关键词：     

单核子在具有八极形变的平均势场中的混沌运动(Ⅲ)初始相干态空时演化中几率密度及扰动强度的研究

运用在二维不对称谐振子势加八极形变势中传播的二维不对称谐振子相干态,研究了不同强度耦合作用下密度矩阵的复杂性及对干扰动强度微小变动的敏感性。发现相应于对应经典系统作规则、部分混沌、及整体混沌运动的相空间区域,量子系统有对应的特征性的表现,它们与势能面上负曲率的存在及负曲率的大小有关系.     

单核子在具有八极形变的平均势场中的混沌运动（III）初始？…

运用在二维不对称谐振子势加八极形变势中传播的二维不对称谐振子相干态，研究了不同强度耦合作用下密度矩阵的复杂性及对于扰动强度微小动的敏感性。发现相应于应经典系统作规则、部分混沌、及整体混沌运动的相空间区域，量子系统有对应的特征性的表现，它们与势能面上负曲率的存在及负曲率的大小有关系。     

（2+1）维动态黑洞的量子熵

在Tortoise坐标系中，利用brick-wall模型研究了来源于标量场的(2+1)维动态黑洞的量子熵.结果表明，在视界附近的薄区域内标量场的熵与黑洞熵有相同结构.特别是在静态情况下，量子熵满足熵的周长律. 关键词： 标量场 brick-wall模型 (2+1)维动态黑洞 量子熵     

二维多量子MAS NMR的计算机模拟研究

最近Frydman等人报道了联合MAS及多量子方法获取半整数四极核各向同性谱的新途径,本文以自旋3/2的四极核为例,采用步进式时序积分手续,数值计算了魔角样品旋转条件下的传播子,从而真实地模拟了非对易含时Hamiltonian情况下的密度矩阵演化;对Fryman等人采用的双脉冲序列实验应采取的最佳条件进行了详尽的理论分析;并对Na₂C₂O₄样品的2D-MQ-MAS实验进行拟谱。     

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．     

1,2-二氢-4-(4-羟基苯基)(2H)二氮杂萘-1-酮的NMR研究

应用多种二维核磁共振谱,即：2D同核化学位移全相关谱(TOCSY),2D NOESY谱,2D 异核多量子相关谱(HMQC)和2D异核¹³C-¹H多键 相关谱(HMBC),对化合物1,2-二氢-4-(4-羟基苯基)(2H)二氮杂萘-1-酮的¹H和¹³C NMR 谱线进行了完整归属,从而系统地分析和讨论了该化合物的结构特征.     

Double-quantum excitation in the NMR of spinning solids by pulse-assisted rotational resonance

We describe a new technique for double-quantum excitation in magic-angle-spinning NMR of powdered solids. The technique is designed to efficiently excite double-quantum coherence in the vicinity of a rotational resonance condition. The offset from rotational resonance allows the double-quantum filtered signals to be observed with high resolution and sensitivity. The method uses rotational excitation of zero-quantum coherence, assisted by radiofrequency pulse cycles. The zero-quantum coherence is converted into double-quantum coherence by a frequency-selective inversion sequence. Experiments on [(13)C(2), (15)N]-glycine demonstrate a double-quantum filtering efficiency of approximately 41% at a sample rotation frequency of 8.300 kHz, which is 1.600 kHz away from the n = 1 rotational resonance. We achieve 32% double-quantum filtering efficiency at a spinning frequency of 9.250 kHz, which is 2.550 kHz away from rotational resonance.     

Efficient double-quantum excitation in rotational resonance NMR

We present a new technique for double-quantum excitation in magic-angle-spinning solid-state NMR. The method involves (i) preparation of nonequilibrium longitudinal magnetization; (ii) mechanical excitation of zero-quantum coherence by spinning the sample at rotational resonance, and (iii) phase-coherent conversion of the zero-quantum coherence into double-quantum coherence by frequency-selective spin inversion. The double-quantum coherence is converted into observable magnetization by reversing the excitation process, followed by a pi/2 pulse. The method is technically simple, does not require strong RF fields, and is feasible at high spinning frequencies. In [(13)C(2),(15)N]-glycine, with an internuclear (13)C-(13)C distance of 0.153 nm, we achieve a double-quantum filtering efficiency of approximately 56%. In [11, 20-(13)C(2)]-all-E-retinal, with an internuclear (13)C-(13)C distance of 0.296 nm, we obtain approximately 45% double-quantum filtering efficiency.     

自旋1/2-自旋1耦合系统的HSQC和HDQC实验的研究

对自旋1/2-自旋1耦合系统的单量子HSQC和双量子HDQC脉冲序列进行了理论和实验的探讨. 研究结果表明,文献提出的HDQC实验中实际上还发生了零量子跃迁,因此该实验应该是多量子HMQC实验. 研究结果还表明,HSQC有比HDQC更高的灵敏度.     

Effective dipolar couplings determined by dipolar dephasing of double-quantum coherences

It is shown how homonuclear distances and homonuclear dipolar lattice sums between spin-1/2 nuclei can be measured by a pulsed solid-state NMR experiment under magic-angle spinning conditions. The presented technique is based on double-quantum coherence filtering. Instead of measuring a build-up of double-quantum coherence the pulse sequence is designed to dephase double-quantum coherence. This is achieved by exciting double-quantum coherence either with the help of the through-space dipolar coupling or the through-bond dipolar coupling while the dephasing relies on the through-space dipolar coupling as selected by a gamma-encoded pulse sequence from the C/R symmetry class. Since dephasing curves can be normalized on zero dephasing, it is possible to analyze the initial dephasing regime and hence determine dipolar lattice sums (effective dipolar couplings) in multiple-spin systems. A formula for the effective dipolar coupling is derived theoretically and validated by numerical calculations and experiments on crystalline model compounds for (13)C and (31)P spin systems. The double-quantum dephasing experiment can be combined with constant-time data sampling to compensate for relaxation effects, consequently only two experimental data points are necessary for a single distance measurement. The phase cycling overhead for the constant-time experiment is minimal because a short cogwheel phase cycle exists. A 2D implementation is demonstrated on [(13)C(3)]alanine.     

Multiple-quantum relaxation in the magic-angle-spinning NMR of 13C spin pairs.

We determine the decay rate constants of zero-, double- and single-quantum coherence for 13C spin pairs in magic-angle-spinning solid-state NMR. The double-quantum coherence is excited by a C7 pulse sequence and converted into zero-quantum coherence by a frequency-selective pair of pi/2 pulses. The zero-quantum coherence is reconverted into observable magnetization by a second pair of pi/2 pulses followed by a second C7 sequence. In a magnetically dilute system where the 13C-13C distance is 0.296 nm, the relaxation rate constants are consistent with a model of uncorrelated random fields at the two labeled 13C sites. In a fully-labelled system with a short 13C-13C distance of 0.153 nm, the measured rate constants are inconsistent with the uncorrelated random field model.     

High-resolution absorptive intermolecular multiple-quantum coherence NMR spectroscopy under inhomogeneous fields

Intermolecular multiple-quantum coherence (iMQC) is capable of improving NMR spectral resolution using a 2D shearing manipulation method. A pulse sequence termed CT-iDH, which combines intermolecular double-quantum filter (iDQF) with a modified constant-time (CT) scheme, is designed to achieve fast acquisition of high-resolution intermolecular zero-quantum coherences (iZQCs) and intermolecular double-quantum coherences (iDQCs) spectra without strong coupling artifacts. Furthermore, double-absorption lineshapes are first realized in 2D intermolecular multi-quantum coherences (iMQCs) spectra under inhomogeneous fields through a combination of iZQC and iDQC signals to double the resolution without loss of sensitivity. Theoretically the spectral linewidth can be further reduced by half compared to original iMQC high-resolution spectra. Several experiments were performed to test the feasibility of the new method and the improvements are evaluated quantitatively. The study suggests potential applications for in vivo spectroscopy.     

Analysis of 1H NMR spectra with the combined use of zero- and double-quantum coherence

Both homonuclear zero-quantum and double-quantum coherence correlation experiments have been suggested previously as alternatives to the standard single-quantum coherence correlation experiment (COSY). However, both those experiments have a number of associated problems, including the difficulty in obtaining uniform excitation of coherence and the size of the data matrix which in both cases may be twice as large, and hence takes twice as long to acquire, as that of the corresponding COSY experiment. Both those problems are substantially alleviated in the approach demonstrated here, which combines the simultaneous acquisition of both types of correlation spectra and the most economical formatting of the data; this is shown to be particularly significant where the F₁ dimension is broadband decoupled. The method is demonstrated at 300 MHz for allyl bromide and dehydrotestosterone.     

Characteristics of zero-quantum correlation spectroscopy in MAS NMR experiments

Zero-quantum coherence generation and reconversion in magic-angle spinning solid-state NMR is analyzed. Two methods are discussed based on implementations using symmetry-based pulse sequences that utilize either isotropic J couplings or dipolar couplings. In either case, the decoupling of abundant proton spins plays a crucial role for the efficiency of the zero-quantum generation. We present optimized sequences for measuring zero-quantum single-quantum correlation spectra in solids, achieving an efficiency of 50% in ubiquitin. The advantages and disadvantages of zero-quantum single-quantum over single-quantum single-quantum correlation spectroscopy are explored, and similarities and differences with double-quantum single-quantum correlation spectroscopy are discussed. Finally, possible application of zero-quantum single-quantum experiments to polypeptides, where it can lead to better spectral resolution is investigated using ubiquitin, where we find high efficiency and high selectivity, but also increased line widths in the MQ dimension.     

Simplifying DOSY spectra with selective TOCSY edited preparation

Diffusion-ordered NMR spectroscopy, while quite powerful, is limited by its inability to resolve signals that are severely overlapped in the proton spectrum. We present here a DOSY experiment that uses selective TOCSY as an editing/preparation period. With this method, well-resolved signals of the analytes are selectively excited and the magnetization subsequently transferred by isotropic mixing to resonances buried in the matrix background, which are then resolved by the ensuing DOSY sequence. Key to the success of our proposed method is the incorporation of a highly effective zero-quantum filter into the selective TOCSY preparation period, which prevents zero-quantum coherence from being carried into the DOSY part of the pulse sequence. Further improvement in spectral resolution can be obtained by expanding the proposed experiment into a 3D sequence and utilizing the homonuclear decoupling feature of the BASHD-TOCSY technique. Both pulse sequences were found to greatly simplify the DOSY spectrum of a 'dirty' sucrose/raffinose mixture, as the complex matrix background is no longer present to obscure or overlap with the signals of interests. Furthermore, complete resolution of the relevant signals was achieved with the 3D sequence.     

Determination of ¹J(⁵⁹Co-⁵⁹Co) scalar coupling constants in the tetrahedral mixed-metal cluster HFeCo₃(CO)₁₀(PCyH₂)(PPh₂[CH₂C(O)Ph]) using COSY-type NMR experiments

Two-dimensional ??Co correlation spectroscopy (COSY) and double-quantum-filtered (DQF) COSY NMR experiments are reported for the tetrahedral mixed-metal cluster HFeCo?(CO)??(PCyH?)(PPh?[CH?C(O)Ph]), which consists from the point of view of ??Co NMR spectroscopy, of an AMX system of three-spin S=7/2. Both 2D NMR spectra prove the existence of a J scalar coupling constant between non-equivalent ??Co nuclei. By contrast to what happens with the conventional 2D ??Co COSY NMR spectrum, it was possible to simulate the 2D ??Co DQF-COSY NMR spectrum by density matrix calculations in order to extract the values of the 1J(??Co-??Co) coupling constants. The comparison between experimental and theoretical 2D NMR spectra gives spin-couplings constants of several hundreds Hertz for this cluster.