Linewidth Analysis of Spin Labels in Liquids: I. Theory and Data Analysis

We present a method of simulating the EPR spectra of spin labels in liquids using direct convolution of hyperfine splitting with Lorentzian linewidths. The aim is to simulate the experimental lineshape by considering all spectrometer characteristics as well as inhomogeneous and homogeneous linewidth effects. A major advance in this method is the correction for the broadening produced by Zeeman modulation commonly used to obtain EPR signals; this allows experimenters much more freedom to optimize their experimental conditions for the best signal-to-noise ratio. Microwave power broadening (saturation) effects on the EPR lines are significant even at very low observer levels. Successful simulation requires that all contributions from unresolved hyperfine splittings be explicitly included. Inhomogeneous broadening is dealt with by including all spins that interact with the electron (as a set of superhyperfine interactions); there is no "effective Gaussian" to substitute for the correct superhyperfine interactions. The effects of spin exchange on the linewidth and lineshape can be observed and must be taken into account in order to extract the fundamental linewidths.     

量子自旋液体的实验研究进展

量子自旋液体是指由于其中存在的强量子涨落导致自旋即使在零温极限下也不形成磁有序的一种新的自旋量子态。区别于传统的磁有序材料,它的基态没有确定的序参量来表示,并且不伴随任何自发的对称性破缺,超越了朗道相变理论所能描述的物相范畴,代表了一种新奇的量子物态,具有非常高的理论研究价值。这一全新的物态被认为与非常规超导机制之间有着十分紧密的关系。同时在未来的量子计算方面有着非常诱人的应用前景,因此一直以来备受关注。虽然量子自旋液体理论经过近半个世纪的积淀有了长足的发展,但是由于候选材料稀少,实验测量条件苛刻等多种因素制约,导致实验方面的进展相对缓慢。近年来各项实验技术的进步和成熟为量子自旋液体候选材料的测量表征提供了有利条件,加快了实验工作的推进速度。本文将从实验的角度介绍 (1) 几何阻挫量子自旋液体候选材料,包括三角晶格化合物 YbMgGaO量子自旋液体是指由于其中存在的强量子涨落导致自旋即使在零温极限下也不形成磁有序的一种新的自旋量子态。区别于传统的磁有序材料,它的基态没有确定的序参量来表示,并且不伴随任何自发的对称性破缺,超越了朗道相变理论所能描述的物相范畴,代表了一种新奇的量子物态,具有非常高的理论研究价值。这一全新的物态被认为与非常规超导机制之间有着十分紧密的关系。同时在未来的量子计算方面有着非常诱人的应用前景,因此一直以来备受关注。虽然量子自旋液体理论经过近半个世纪的积淀有了长足的发展,但是由于候选材料稀少,实验测量条件苛刻等多种因素制约,导致实验方面的进展相对缓慢。近年来各项实验技术的进步和成熟为量子自旋液体候选材料的测量表征提供了有利条件,加快了实验工作的推进速度。本文将从实验的角度介绍(1)几何阻挫量子自旋液体候选材料,包括三角晶格化合物YbMgGaO_4和YbZnGaO_4、κ-(BEDT-TTF)_2Cu_2(CN)_3、EtMe_3Sb[Pd(dmit)_2]_2和kagome格子化合物ZnCu_3(OH)_6Cl_2;(2)Kitaev量子自旋液体候选材料铱氧化物(Na_2IrO_3与α-,β-,γ-Li_2IrO_3)和α-RuCl_3。文章将着重介绍近年来在量子自旋液体实验方面的进展,之后做一个简单的总结,最后对量子自旋液体的未来发展做一个展望。     

Fast and accurate characterization of biological membranes by EPR spectral simulations of nitroxides

A method by which it is possible to characterize the membranes of biological samples on the basis of the EPR spectral lineshape simulation of membrane-dissolved nitroxide spin probes is described. The presented simulation procedure allows the determination of the heterogeneous structure of biological membranes and fluidity characteristics of individual membrane domains. The method can deal with isotropic and anisotropic orientations of nitroxides introduced into the biological samples described by restricted fast motion with a correlation time between 0.01 and 10 ns. The linewidths of the Lorentzian lineshapes are calculated in a restricted fast-motion approximation. In the special case of samples with high concentrations of nitroxides or in the presence of paramagnetic ions, the lineshapes are calculated directly from the exchange-coupled Bloch equations. The parameters describing ordering, relaxation, polarity, and the portions of the individual spectral components are extracted by optimizing the simulated spectra to the experimental spectrum with either a Simplex or a Monte Carlo algorithm. To improve the algorithm's efficiency, a new way of characterizing the goodness of fits is introduced. The new criterion is based on the standard least-squares function, but with special weighting of the partial sums. Its benefits are confirmed with membrane spectral simulation. Two classes of examples-simulation and optimizations of synthetic spectra to evaluate the accuracy of the optimization algorithms and simulation and optimization of EPR spectra of nitroxides in liposome suspensions in the presence of a broadening agent and in human leukocytes are shown.     

光参量振荡器线宽研究

对０．５３２μｍ波长光泵浦的ＢＢＯ光参量振荡器产生线宽的机制进行了详细分析和计算，结果与实验基本一致，实验结果表明泵浦光发散角是产生线宽的主要因素。文中的分析方法可推广至其它单轴晶体光参量振荡器线宽的分析。     

全频域下窄线宽激光器光谱线宽的分析

窄线宽激光器的线宽表征方式通常采用延时自外差法测量技术。该技术是通过延时光纤差拍产生一个与待测激光线宽相关的洛伦兹频谱,因此该频谱只具有单一的线宽表现形式。为了能够观察到激光器的线宽和频率噪声在其傅里叶频率分布下的完整特性,报道了一种基于β算法计算窄线宽激光器线宽的方法。该方法是结合频率噪声中的白噪声和1/f噪声分别诱导不同激光线型的理论,从而确定激光线宽。首先,对β算法的基本原理进行了详细的分析说明。通过基于维纳-辛钦定理,分析了窄线宽激光器不同频率范围内的频率噪声和激光线宽的依赖关系。阐明了在截止频率趋于0和无穷大的两个范围条件时,激光频谱特性从高斯线型向洛伦兹线型演变。同时推导出使两种线型转换的截止频率表达式,并将其转换为频率噪声函数,该函数定义为β分子线。此时频率噪声分量中高斯线型的总和即为激光线宽计算公式;其次,对窄线宽激光器的频率噪声和激光线型进行数值仿真。将通过OEwaves公司的OE4000互相关零差相位/频率噪声自动测试系统测得的频率噪声谱密度,带入β算法理论公式中。结果显示：1/f噪声导致激光呈现高斯线型,线宽随截止频率的增加而增大。而白噪声将导致洛伦兹线型,线宽不再随截止频率而改变。此外,在低频区域,频率噪声电平远大于其傅里叶频率,噪声调制系数较高,该部分噪声可以决定线宽大小。因此,高斯线型区域对应的频率噪声的积分,即为待测激光器的线宽;在高频区域,频率噪声电平与其傅里叶频率相差较小,频率波动较快,噪声对线宽影响可以忽略。并且频率带宽在截止频率范围内,计算的线宽误差较小。最后,实验上运用β算法对RIO公司的1 550 nm低噪声窄线宽激光器的频率噪声功率谱密度进行积分计算,成功获得了其不同傅里叶频率分布下对应的激光线宽值。其中β分子线将频率噪声中的白噪声和1/f噪声分隔两部分：当频率噪声谱密度大于β分子线时,激光即为高斯线型,线宽随频率积分带宽的增加而减少;而频率噪声谱密度小于β分子线时,激光呈现洛伦兹线型,线宽为定值不再改变。同时为了对β算法进行实验验证,搭建了延迟光纤为50 km、移频频率为60 MHz的延时自外差法测量系统。对注入电流为110 mA的RIO 1 550 nm低噪声窄线宽激光器的线宽进行实验测量,测量结果表明激光线宽为1.8 kHz,与上述β算法中2.8 kHz的频率带宽积分结果一致。充分证明了此算法的准确性。β算法可以对任意类型的窄线宽激光器进行线宽表征,对窄线宽激光器的研究具有重要意义。     

中国自由基捕获技术发展30年

本文简要回顾了30年来国内在自由基捕获技术（spin trapping）领域的研究进展,其中包括新型自由基捕获探针的分子设计与合成,探针结合EPR波谱方法在光、电化学反应以及生物领域的应用实例. 最后,结合国内外自由基捕获技术现状讨论了它的未来发展前景.     

皮秒级BBO晶体光参量发生放大器中线宽的分析与计算

采用全量子理论，建立了皮秒级光参量发生放大器中自发参量辐射产生参量光线宽的数学方程，并对影响参量光线宽的各种物理机制进行计算机模拟、分析和比较。其结果是：在远离简并点时，所产生的参量光线宽很小，而在简并点附近，参量光线宽急剧增大；且泵浦光的发散角和在偏轴方向的泵浦光对参量光线宽的影响较大。这些结果对压缩光参量激光器的线宽具有重要的意义。     

Spin Hall Magnetoresistance and Spin Nernst Magnetothermopower in a Rashba System: Role of the Inverse Spin Galvanic Effect

In ferromagnet/normal‐metal bilayers, the sensitivity of the spin Hall magnetoresistance and the spin Nernst magnetothermopower to the boundary conditions at the interface is of central importance. In general, such boundary conditions can be substantially affected by current‐induced spin polarizations. In order to quantify the role of the latter, we consider a Rashba two‐dimensional electron gas with a ferromagnet attached to one side of the system. The geometry of such a system maximizes the effect of current‐induced spin polarization on the boundary conditions, and the spin Hall magnetoresistance is shown to acquire a non‐trivial and asymmetric dependence on the magnetization direction of the ferromagnet.     

Spin & statistics in nonrelativistic quantum mechanics,II

Recently a sufficient and necessary condition for Pauli's spin‐statistics connection in nonrelativistic quantum mechanics has been established [1]. The two‐dimensional part of this result is extended to n‐particle systems and reformulated and further simplified in a more geometric language.     

利用自差法研究激光二极管泵浦Nd:YVO_4激光器的线宽

用光纤延时自差法测量二极管激光纵向泵浦单频运转的Nd：YVO4激光器的线宽。在1秒时间内，激光线宽为25kHz。还测量了线宽与激光器腔长和输出功率的关系。     

离焦写入线宽的动态高斯模型

为提高集成光学器件中的多线宽制作效率,提出了基于激光直接写入技术的离焦加工模式,即加工时激光束的聚焦点不落在胶层表面而是在其前方或后方;同时还建立了基于多个加工参量的线宽数学模型。此线宽模型首先假定激光束经物镜变换后,在像方任意离焦面上的能量仍保持高斯分布,其次还考虑了光束动态扫描引起的光斑线度对曝光能量分布的影响,故称其为动态高斯模型。此线宽模型涉及光功率、基片离焦量、光束扫描速度、胶层曝光能量阈值等加工参量。对线宽模型的验证在自行研发的极坐标型激光图形发生器上进行,实验表明:相对于不考虑光斑运动的静态高斯模型,动态高斯模型更为符合实验结果。     

135La高自旋态的实验研究

利用在束γ谱实验技术,通过¹²⁸Te(¹⁰B,3n)¹³⁵La反应研究了¹³⁵La的高自旋态.基于γγ符合关系、γ射线的相对强度和各向异性度的测量结果,建立了¹³⁵La的能级纲图.在hω≈0.40MeV附近,观测到基于πh_11/2质子轨道上的负宇称带的带交叉.比较N=78同中子素链能级结构的系统性,认为该带交叉是由一对h_11/2准质子发生转动顺排造成的.在高自旋态处,观测到具有很强M1跃迁、Signature劈裂很小的ΔI=1负宇称带,根据系统性认为该带是建立在πh_11/2(νh_11/2)²组态上的γ≈–60°的扁椭球形变带.     

Anisotropic ESR parameters of Cu(II) complexes in solutions and dynamics of solvent coordination: use of “minimum linewidths”

The “minimum linewidths” seen in the ESR linewidths against temperature plots, the dependence of line widths on the⁶³Cu nuclear magnetic quantum numbers and the Hubbard relation provide sufficient number of equations to determine the anisotropic ESR parameters in the case of axially symmetric Cu(II) complexes even when unresolved hyperfine structures make contributions to linewidths. After testing the method by reanalysing the literature data on Cu(II) bis-acetylacetonate, it has been used to obtain the anisotropic ESR parameters in the case of bis-salicylaldehydate of Cu(II). Linewidth contributions from unresolved hyperfine structures associated with the¹H of coordinating CHCl₃ inferred in these studies, were confirmed by comparing the widths in CHCl₃ and CDCl₃ under ideal conditions. The temperature dependence of this contribution and the estimate of rate constant at room temperature (∼ 10¹⁰ s⁻¹) suggest that the coordinating solvent exchange is diffusion controlled.     

Linewidth of electromagnetically induced transparency under motional averaging in coated vapor cell

The linewidth of electromagnetically induced transparency (EIT) in a coated Rb vapor cell was studied under a magnetic field gradient. The nonlinear broadening of the EIT linewidth with the magnetic field gradient was observed. It was found that the motional averaging of the field gradient was more pronounced at higher laser intensities and larger beam sizes. In the same regime, there was a small linewidth decrease with the increasing magnetic field gradient. We have established a Monte-Carlo model, which gave results in good qualitative agreement with our experiment. Physics pictures for the above phenomena were also suggested. These results provide an understanding of the EIT linewidth behavior under the motional averaging, and should be useful for applications in quantum optics and metrology based on coated vapor cells.     

Electron spin polarisation in the photoreduction of xanthone in alcohol: effect of concentration and temperature

Time-resolved EPR studies of the hydrogen abstraction reaction of photoexcited xanthone in 2-propanol were carried out as a function of the concentration of xanthone and the sample temperature. The temperature was varied from 22°C to about ?30°C, and the concentration from about 0.2 to 4.0?mM. At low temperature or concentration, the observed spectra of the xanthone ketyl radical and the propan-2-olyl radical could be simulated as a superposition of a hyperfine-independent component due to the emissive triplet mechanism and a hyperfine-dependent component due to the S–T₀ radical pair mechanism. However, with an increase in the concentration of xanthone, the relative contribution of TM decreases, and, concomitantly, the net absorptive component of only the xanthone ketyl radical increases. As the spin polarisation mechanisms do not predict any concentration dependence, this unusual behaviour is explained by invoking the enhancement of the spin–lattice relaxation rates due to Heisenberg spin exchange occurring at high local concentrations of the radicals. The net absorptive signal is attributed to thermally equilibrated radicals. The observed temperature dependence of the spin polarisation behaviour is similarly explained. The origin of the net absorptive signal in the TREPR spectra of the acetone?2-propanol system is also attributed to thermally equilibrated radicals. The self-quenching mechanism of xanthone is proposed to be an electron-transfer reaction from an excited xanthone molecule to another xanthone in the ground state.     

微波电子自旋共振实验波形分析

详细分析了微波段用可调反射式谐振腔做电子自旋共振实验中共振信号的形成原理,分析指出下凹和上凸波形都为共振吸收信号,当波形的上下两部分等大时,为色散信号,波形的上下两部分不等大时,为色散信号和共振吸收信号的合成。从理论上解释了共振信号的变化所反映的物理过程。     

Two-Photon Exchange Corrections to Single Spin Asymmetry of Neutron and 3He

In a simple hadronic model, the two-photon exchange contributions tothe single spin asymmetries for the nucleon and the ³He are estimated. The results show that the elastic contributions of two-photon exchange to the single spin asymmetries for the nucleon are rather small while those for the ³He are relativelylarge. Besides the strong angular dependence, the two-photon contributions to the single spin asymmetry for the ³He are very sensitive to the momentum transfer.     

电场对量子阱中自由载流子光辐射线宽的影响

本文对固体中在较大空间范围运动的粒子采用轨道、动量及波包来描述。根据量子力学测不准关系, 粒子的能量测不准公式被导出。公式表明, 电场强烈地散射载流子, 使载流子所处能级大为展宽。应用该公式到Ｐ－Ｉ－Ｎ结构的ＧａＡｓ／ＧａＡｌＡｓ 多量子阱中, 理论计算的光辐射线宽与光致荧光实验测得的线宽吻合。     

Linewidth of electromagnetically induced transparency under motional averaging in a coated vapor cell

The linewidth of electromagnetically induced transparency(EIT) in a coated Rb vapor cell was studied under a magnetic field gradient.The nonlinear broadening of the EIT linewidth with the magnetic field gradient was observed.It was found that the motional averaging of the field gradient was more pronounced at higher laser intensities and larger beam sizes.In the same regime,there was a small linewidth decrease with the increasing magnetic field gradient.We have established a Monte-Carlo model,which gave results in good qualitative agreement with our experiment.Physics pictures for the above phenomena were also suggested.These results provide an understanding of the EIT linewidth behavior under motional averaging,and should be useful for applications in quantum optics and metrology based on coated vapor cells.