三维量子自旋玻璃理论(Ⅰ)——稳态Replica对称近似

利用虚时泛函积分技术和Replica方法,建立了具有Dazyaloshinskii-Moriya各向导性和铁磁相互作用的三维量子自旋玻璃理论。在稳态Replica对称近似下,确定了自旋自相互作用、自旋玻璃序参量和磁化强度的自洽方程组,获得了对角磁化率与序参数间的关系,给出了与序参数有关的自由能密度,克服了有关理论的低温失效。 关键词：     

一种从EPR粉末谱精确提取自旋哈密顿及线型参数的拟合方法

本文提出一种从EPR粉末谱精确提取自旋哈密顿和线型参数的拟合方法,适用于不同单晶线型和哈密顿。该方法不但可用于共振磁场能解析表示的情形,而且也可用于共振磁场只能通过对角化哈密顿数值解出的情形。     

铯原子介质中受激拉曼四波混频的光放大特性

实验研究了在铯原子介质中受激拉曼四波混频过程中,注入的探针光与所产生的共轭光的增益特性,具体比较了在探针场分别作为Stokes场和Anti-Stokes场情况下,增益随粒子数密度、泵浦光频率失谐的依赖关系,并分析了其增益谱线线型和谱宽.为进一步开展基于受激拉曼四波混频进行量子关联光束的制备提供了主要实验参数的选择参考.     

基于谱线线型函数的气体浓度检测技术

快速、精确地测量微量气体浓度的技术在大气质量分析、环境污染检测等领域具有广泛的用途。在红外光谱检测技术中,气体吸收光谱的谱线线型函数是定量测量气体浓度的一个重要参量,而如何准确和快速地得到气体谱线线型函数值是气体浓度测量中的一个关键问题。首先从理论上分析了谱线线型函数,得出计算谱线线型函数的一般方法及探讨了气体浓度与谱线线型函数峰值之间的关系。然后,利用可调激光器及光谱仪检测系统测量了乙炔在1 515～1 545 nm波长范围内的吸收光谱,再通过Lambert-Beer定律计算得到在不同频率下的谱线线型函数峰值,最后利用程序拟合出该波段内气体的谱线线型函数峰值分布曲线,并与Voigt线型函数理论计算值进行了比较,发现理论计算的谱线线型函数峰值仍存在一定的偏差。相比理论计算结果,所提出的检测方法得到的乙炔浓度与真实的乙炔浓度值更加吻合,表明了通过实验确定的谱线线型函数的经验公式可以更好地用于气体浓度的检测。由于利用实验测量值获得了谱线线型函数峰值分布的拟合曲线,因此可以快速准确地计算出所对应的谱线线型函数峰值,从而大大地简化了线型函数的计算过程。实验所获得的数据可应用于光学遥测乙炔气体浓度,且提供的方法也可以应用到其他气体的谱线线型函数峰值的测量中。     

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,βLD=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.     

晶体Zn（antipyrine）2（NO3）2∶VO^2＋的EPR谱及光吸收谱的理论研究

由于硝酸钒锌二安替比林晶体[Zn(antipyrine)2(NO3)2∶VO2 ]中配体O2-的自旋-轨道耦合参量0pζ≈150cm-1与中心过渡族3d1离子V4 的ζ0d≈248 cm-1相差不太大,故配体的自旋-轨道耦合参量0pζ对电子顺磁共振(EPR)谱和光吸收谱的贡献必须考虑。采用双自旋-轨道耦合参量模型和相关的晶体场能级公式,计算了Zn(antipyrine)2(NO3)2∶VO2 晶体的EPR谱和光吸收谱,所得理论结果与实验发现很好符合;确定了该晶体的局域对称结构沿C4轴的四角畸变约为0.45 nm;计算发现,较大的κ值说明VO2 中未配对的s电子对超精细结构常数有较大的贡献。并对上述这些结果的合理性进行了讨论。     

晶体Zn(antipyrine)2(NO3)2:VO2+的EPR谱及光吸收谱的理论研究

由于硝酸钒锌二安替比林晶体[Zn(antipyrine)2(NO3)2:VO2 ]中配体O2-的自旋-轨道耦合参量ζ0p≈150 cm-1与中心过渡族3d1离子V4 的ζ0d≈248 cm-1相差不太大,故配体的自旋-轨道耦合参量ζ0p对电子顺磁共振(EPR)谱和光吸收谱的贡献必须考虑.采用双自旋-轨道耦合参量模型和相关的晶体场能级公式,计算了Zn(antipyrine)2(NO3)2:VO2 晶体的EPR谱和光吸收谱,所得理论结果与实验发现很好符合;确定了该晶体的局域对称结构沿C4轴的四角畸变约为0.45 nm;计算发现,较大的κ值说明VO2 中未配对的s电子对超精细结构常数有较大的贡献.并对上述这些结果的合理性进行了讨论.     

微米气室铯原子自旋噪声谱

利用自旋噪声谱技术研究了无缓冲气体133Cs原子气室的自旋动力学和展宽机制.在宏观原子气室中,自旋弛豫速率失谐频率谱的线型为高斯分布;在空间局域较强的微米气室中,自旋弛豫速率失谐频率谱的线型为洛伦兹分布.实验测量得到的自旋弛豫速率失谐频率谱的展宽约4 GHz,明显大于宏观原子气室中约度强烈依赖于激光相对于原子共振跃迁的频率失谐;在微米气室中,由于较强的均匀展宽,总噪声的失谐频率谱中心处出现明显的凹陷.通过建立简化的物理模型来计算微米气室的展宽机制,在实验与理论中解释了原子的均匀展宽特性.     

速度调制分子离子激光光谱技术的理论研究

介绍了速度调制光谱对分子离子测量过程中的一些基本问题,运用朗之万运动方程导出了离子在交流电场中的漂移速度表达式;在小调制度近似下,给出了速度调制谱线的解析表达式,表明谱线的基本线型为高斯线型的一次微分线型、强度与调制度成正比;还讨论了调制电场对谱线的影响。得到的结论可用于实验参数的选择及等离子体的诊断等方面。     

烷烃相变过程的拉曼光谱研究

利用激光拉曼光谱监测正二十烷相变过程中的有序无序变化。发现位于1 300 cm-1处谱峰的积分强度在相变温度区间发生较大变化,这与以前相关的理论及实验工作存在较大区别,由此讨论了1 300 cm-1谱峰在有机物及生物膜结构的拉曼光谱实验中作为参考峰的局限性。此外,由于序参量可以定量的标定有机物及生物膜结构中各种有序无序结构的含量,所以成为现在拉曼光谱研究中的一个热点问题。Meier对于有机物拉曼光谱研究中长时间以来一直使用的序参量定义提出了质疑,文章的相关实验支持了Meier的看法,并从实验证据上表明了惯用序参量定义的有限性。     

晶体CsMgCl3:Ni2+的局部结构、光谱和EPR谱的理论研究

本文采用半自洽场(semi-SCF) 自由Ni2+的3d轨道波函数、点电荷-偶极子模型和Ni2+-6X-(X=F,Cl,Br,I)络合物的μ-κ-α模型,建立了结构参数与光谱、EPR谱之间的定量关系,利用完全对角化方法,由光谱和电子顺磁共振(EPR)谱,确定了CsMgCl3:Ni2+晶体的局部结构参数,统一解释了CsMgCl3:Ni2+晶体的吸收光谱和EPR 谱.此外,还讨论了高阶微扰方法、参量拟合方法等问题.理论计算结果与实验值符合得很好.     

Investigation of the molecular motion of spin-labeled lysozyme in solution by the use of ESP spectra and electron spin relaxation

The theory of electron spin relaxation in protein solutions taking into account the “two-motion” model of spin label mobility is developed. The relations obtained for the longitudinal and transverse relaxation rates describe the experimental results better than isotropic (“one-motion”) model. The mechanism of longitudinal relaxation in solution of spin-labeled lysozyme is revealed and the correlation time of the inherent motion of spin label is evaluated. The linewidth analysis and study of ESR spectra under viscosity variation were used to obtain the microdynamical parameters characterizing lysozyme molecular mobility. A discrepancy between the correlation time values obtained by viscosity-variation-technique and the results known from other methods is found and ascribed to the manifestation of the intermediate time-scale mobility of protein.     

Influence of the molecular structure of components on the induction of mesophases in nematic liquid crystal systems

The dielectric properties of nematic liquid crystals (NLC) are studied in the temperature range of mesophase existence with taking into account the peculiarities of the molecular structure of components. The dependence of the ordering parameter and activation energy on the temperature and composition of an LC system are obtained and investigated by analysis of EPR spectra based on the spin relaxation theory. The values of the local viscosity of the systems are estimated within the framework of the hydrodynamic model. The appearance of induced and reentrant mesophases is established. It is shown that in NLC systems with non-center-symmetric molecules the correlation between the activation energy and thermostability should be inverse to that in the Maier-Saupe model.     

Spectroscopic Studies on Threonine Doped Polyaniline Composites

The structural and magnetic properties of polyaniline (PANI)- and threonine (T)-doped polyaniline composites were characterized by using FTIR, UV-Vis, and electron paramagnetic resonance (EPR) spectroscopic techniques. The FTIR, UV-Vis, and X-band EPR spectra were recorded for PANI- and threonine-doped polyaniline (PANI-T) composites. The increased intensity of the IR bands in PANI-T composites is due to the increasing dopant concentration. The observed red shift corresponding to the N-H ··· N mode indicates the hydrogen bond formation in between the PANI and threonine molecule. The observed decrease in spectral intensity of the UV-Vis spectrum of the PANI-T composite confirms the occurrence of the protonation at the imine nitrogen sites. The EPR parameters such as line width, g factor, line asymmetry parameter, signal intensity, and spin concentration values were estimated. The EPR spectrum of PANI clearly indicates the presence of unpaired polaron. The EPR signal intensity and spin concentration values decrease with increasing dopant concentration, which reveals the polaron to bipolaron formation in PANI-T composites. EPR lineshape analysis showed that the absorption profile was Gaussian shape. The Gaussian-shaped line is generally due to the dipole–dipole interactions in the PANI and PANI-T composites. The line asymmetry parameter and g values indicated the isotropic nature of PANI and PANI-T composites.     

Quantitative analysis of dinuclear manganese(II) EPR spectra

A quantitative method for the analysis of EPR spectra from dinuclear Mn(II) complexes is presented. The complex [(Me(3)TACN)(2)Mn(II)(2)(mu-OAc)(3)]BPh(4) (1) (Me(3)TACN=N, N('),N(")-trimethyl-1,4,7-triazacyclononane; OAc=acetate(1-); BPh(4)=tetraphenylborate(1-)) was studied with EPR spectroscopy at X- and Q-band frequencies, for both perpendicular and parallel polarizations of the microwave field, and with variable temperature (2-50K). Complex 1 is an antiferromagnetically coupled dimer which shows signals from all excited spin manifolds, S=1 to 5. The spectra were simulated with diagonalization of the full spin Hamiltonian which includes the Zeeman and zero-field splittings of the individual manganese sites within the dimer, the exchange and dipolar coupling between the two manganese sites of the dimer, and the nuclear hyperfine coupling for each manganese ion. All possible transitions for all spin manifolds were simulated, with the intensities determined from the calculated probability of each transition. In addition, the non-uniform broadening of all resonances was quantitatively predicted using a lineshape model based on D- and r-strain. As the temperature is increased from 2K, an 11-line hyperfine pattern characteristic of dinuclear Mn(II) is first observed from the S=3 manifold. D- and r-strain are the dominate broadening effects that determine where the hyperfine pattern will be resolved. A single unique parameter set was found to simulate all spectra arising for all temperatures, microwave frequencies, and microwave modes. The simulations are quantitative, allowing for the first time the determination of species concentrations directly from EPR spectra. Thus, this work describes the first method for the quantitative characterization of EPR spectra of dinuclear manganese centers in model complexes and proteins. The exchange coupling parameter J for complex 1 was determined (J=-1.5+/-0.3 cm(-1); H(ex)=-2JS(1).S(2)) and found to be in agreement with a previous determination from magnetization. The phenomenon of exchange striction was found to be insignificant for 1.     

Magnetic-field-induced orientation of photosynthetic reaction centers as revealed by time-resolved W-band EPR of spin-correlated radical paris: Development of a molecular model

Spin-correlated radical pairs are the short-lived intermediates of the primary energy conversion steps of photosynthesis. In this paper, we develop a comprehensive model for the spin-polarized electron paramagnetic resonance (EPR) spectra of these systems. Particular emphasis is given to a proper treatment of the alignment of the photosynthetic bacteria by the field of the EPR spectormeter. The model is employed to analyze time-resolved W-band (94 GHz) EPR spectra of the secondary radical pair P ₇₀₀ ⁺ A ₁ ^? in photosystem I formed by photoexcitation of the deuterated and¹⁵N-substituted cyanobacteriumSynechococcus lividus. Computer simulations of the angular-dependent EPR spectra of P^700/+A_1/? provide values for the order parameter of the cyanobacterial cells and for the orientation of the membrane normal in a molecular reference system. The order parameter from EPR compares favorably with corresponding data from electron microscopy obtained for theS. lividus cells under similar experimental conditions. It is shown that high-field EPR of a magnetically aligned sample in combination with the study of quantum beat oscillations represents a powerful structural tool for the short-lived radical pair intermediates of photosynthesis.     

Membrane fluidity profiles as deduced by saturation-recovery EPR measurements of spin-lattice relaxation times of spin labels

There are no easily obtainable EPR spectral parameters for lipid spin labels that describe profiles of membrane fluidity. The order parameter, which is most often used as a measure of membrane fluidity, describes the amplitude of wobbling motion of alkyl chains relative to the membrane normal and does not contain explicitly time or velocity. Thus, this parameter can be considered as nondynamic. The spin-lattice relaxation rate () obtained from saturation-recovery EPR measurements of lipid spin labels in deoxygenated samples depends primarily on the rotational correlation time of the nitroxide moiety within the lipid bilayer. Thus, can be used as a convenient quantitative measure of membrane fluidity that reflects local membrane dynamics. profiles obtained for 1-palmitoyl-2-(n-doxylstearoyl)phosphatidylcholine (n-PC) spin labels in dimyristoylphosphatidylcholine (DMPC) membranes with and without 50 mol% cholesterol are presented in parallel with profiles of the rotational diffusion coefficient, R_⊥, obtained from simulation of EPR spectra using Freed’s model. These profiles are compared with profiles of the order parameter obtained directly from EPR spectra and with profiles of the order parameter obtained from simulation of EPR spectra. It is shown that and R_⊥ profiles reveal changes in membrane fluidity that depend on the motional properties of the lipid alkyl chain. We find that cholesterol has a rigidifying effect only to the depth occupied by the rigid steroid ring structure and a fluidizing effect at deeper locations. These effects cannot be differentiated by profiles of the order parameter. All profiles in this study were obtained at X-band (9.5 GHz).     

Electron spin resonance of symmetrical three-spin systems in nematic liquid crystals

An E.S.R. line-shape model is developed for fast tumbling three-spin systems in nematic liquid crystals. The line positions are calculated from a spin hamiltonian, which considers Zeeman, exchange, dipolar and hyperfine interactions of the three unpaired electrons. The dominant spin relaxation process, determining the line-widths, is assumed to result from the anisotropy of the zero-field splitting coupled to the molecular motion. The predictions of the theory are tested by comparison with the temperature-dependent E.S.R. spectra of trisverdazyl radicals in 4,4′-azoxydianisole. Good agreement is found between experimental and simulated spectra. A detailed analysis provides values for the solute order parameters [Pbar] ₂ and [Pbar] ₄. They correspond surprisingly well to predictions of the molecular-field theories of nematic liquid crystals.     

Time-resolved EPR study of electron spin polarization and spin exchange in mixed solutions of porphyrin stable free radicals

The time-resolved electron paramagnetic resonance (EPR) spectra are studied in the temperature range of 110–300 K for two mixed solutions of porphyrins, ZnTPP and H₂TPP, in toluene and the stable free radical 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO). The EPR spectra and their kinetic behavior were studied for concentrations of TEMPO varied in the interval from 0.51 to 7.68 mM, while the porphyrin concentration was fixed as 1 mM. The EPR spectra of triplet-state porphyrins and free radicals manifest the chemically induced spin polarization. For the relatively short-lived radical-triplet pairs, with the perturbation theory up to the fourth order, the theoretical expressions are obtained for the triplet and radical spin polarization induced by the enhanced intersystem crossing (ISC) due to the interaction of excited singlet-state porphyrins with free radicals and by the triplet quenching by free radicals. The time-dependent EPR spectra of the triplets are simulated taking into account the spin-lattice relaxation. It is shown that the variation of the triplet EPR spectra shape, when the time of observation increases, arises from the spin-lattice relaxation kinetics. The kinetic behavior of the TEMPO EPR spectrum was simulated on the basis of the kinetic scheme suggested earlier in the literature. The triplet spin-lattice relaxation time, the rate of the ISC and the lifetime of the excited singlet state were estimated by fitting the kinetic curves for the triplet EPR spectra intensity. For the mixed porphyrin-TEMPO solutions, a possible set of the rate constants of important bimolecular processes were determined. For this set of parameters, it turns out that the spin polarization transfer has a smaller rate constant than the rate constant of the diffusion collisions of the triplet and radical. It appears that the rate constant of the ISC catalyzed by radicals is relatively high in the solutions close to the melting point of the solvent and in the soft-glassy state. In the triplet porphyrins the initial spin polarization induced by the spin-selective ISC was found to exceed the equilibrium spin polarization by up to two orders of magnitude.     

Magnetic resonance study of Ce and Gd doped NiFe2O4 nanoparticles

Present work is a study of temperature dependent electron paramagnetic resonance spectra of Ce and Gd doped nickel ferrite nanoparticles. The samples, synthesised by chemical route were characterised by X-ray diffractometer, electron paramagnetic resonance spectroscopy (EPR) and vibrating sample magnetometer (VSM). The average crystallite size of pure nickel ferrite is ∼64 nm and for Gd and Ce doped samples it is ∼20 nm and ∼14 nm, respectively. The EPR spectra were recorded from 120 to 300 K. Doping with Gd and Ce reduces the line width and g-value in comparison to that of pure nickel ferrite. Ce doped samples have the lowest values of both these parameters at room temperature. This indicates that Ce doped samples show lowest loss and is suitable for high frequency devices. EPR spin numbers are reduced while the spin relaxation time is increased after doping with rare earth ions. Gd doped samples have higher values of relaxation time and lower spin numbers in comparison to that of Ce doped samples. VSM results show that the magnetisation and coercivity are reduced after doping with both Ce and Gd rare earth ions.