Electron spin relaxation of copper(II) complexes in glassy solution between 10 and 120 K

The temperature dependence, between 10 and 120 K, of electron spin-lattice relaxation at X-band was analyzed for a series of eight pyrrolate-imine complexes and for ten other copper(II) complexes with varying ligands and geometry including copper-containing prion octarepeat domain and S100 type proteins. The geometry of the CuN4 coordination sphere for pyrrolate-imine complexes with R=H, methyl, n-butyl, diphenylmethyl, benzyl, 2-adamantyl, 1-adamantyl, and tert-butyl has been shown to range from planar to pseudo-tetrahedral. The fit to the recovery curves was better for a distribution of values of T1 than for a single time constant. Distributions of relaxation times may be characteristic of Cu(II) in glassy solution. Long-pulse saturation recovery and inversion recovery measurements were performed. The temperature dependence of spin-lattice relaxation rates was analyzed in terms of contributions from the direct process, the Raman process, and local modes. It was necessary to include more than one process to fit the experimental data. There was a small contribution from the direct process at low temperature. The Raman process was the dominant contribution to relaxation between about 20 and 60 K. Debye temperatures were between 80 and 120 K. For samples with similar Debye temperatures the coefficient of the Raman process tended to increase as gz increased, as expected if modulation of spin-orbit coupling is a major factor in relaxation rates. Above about 60 K local modes with energies in the range of 260-360 K (180-250 cm-1) dominated the relaxation. For molecules with similar geometry, relaxation rates were faster for more flexible molecules than for more rigid ones. Relaxation rates for the copper protein samples were similar to rates for small molecules with comparable coordination spheres. At each temperature studied the range of relaxation rates was less than an order of magnitude. The spread was smaller between 20 and 60 K where the Raman process dominates, than at higher temperatures where local modes dominate the relaxation. Spin echo dephasing time constants, Tm, were calculated from two-pulse spin echo decays. Near 10 K Tm was dominated by proton spins in the surroundings. As temperature was increased motion and spin-lattice relaxation made increasing contributions to Tm. Near 100 K spin-lattice relaxation dominated Tm.     

Frequency dependence of electron spin relaxation for threeS = 1/2 species doped into diamagnetic solid hosts

Electron spin lattice relaxation rates (1/T₁) were measured as a function of temperature at two or three microwave frequencies for threeS = 1/2 species in temperature ranges with different dominant relaxation processes. Between 10 and 50 K the contribution from the direct process to the relaxation rate was substantially greater at 94 than at 9.5 GHz for a vanadyl porphyrin doped into zinc tetratolylporphyrin. For bis(diethyldithiocarbamato)copper(II) doped into the diamagnetic Ni(II) analog the relaxation rate between 25 and 100 K is dominated by the Raman process and exhibits little frequency dependence between 9.2 and 94 GHz. For 4-hydroxy-2,2,6,6-tetramethylpiperidinoloxy (tempol) doped into a diamagnetic host the relaxation rate between about 40 and 100 K is dominated by the Raman process. In this temperature range, relaxation rates at 3.2, 9.2, and 94 GHz exhibit little frequency dependence. Above about 130 K, the relaxation rate for tempol decreases in the order S-band s> X-band > W-band. The relaxation rates in this temperature range fit a model in which 1/T₁ is dominated by a thermally activated process that is assigned as rotation of the methyl groups on the nitroxyl ring.     

Electron spin-lattice relaxation of nitroxyl radicals in temperature ranges that span glassy solutions to low-viscosity liquids

Electron spin-lattice relaxation rates, 1/T1, at X-band of nitroxyl radicals (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidin-1-oxyl, 3-carbamoyl-2,2,5,5-tetramethylpyrrolidin-1-oxyl and 3-carbamoyl-2,2,5,5-tetramethylpyrrolin-1-oxyl) in glass-forming solvents (decalin, glycerol, 3-methylpentane, o-terphenyl, 1-propanol, sorbitol, sucrose octaacetate, and 1:1 water:glycerol) at temperatures between 100 and 300K were measured by long-pulse saturation recovery to investigate the relaxation processes in slow-to-fast tumbling regimes. A subset of samples was also studied at lower temperatures or at Q-band. Tumbling correlation times were calculated from continuous wave lineshapes. Temperature dependence and isotope substitution (2H and 15N) were used to distinguish the contributions of various processes. Below about 100K relaxation is dominated by the Raman process. At higher temperatures, but below the glass transition temperature, a local mode process makes significant contributions. Above the glass transition temperature, increased rates of molecular tumbling modulate nuclear hyperfine and g anisotropy. The contribution from spin rotation is very small. Relaxation rates at X-band and Q-band are similar. The dependence of 1/T1 on tumbling correlation times fits better with the Cole-Davidson spectral density function than with the Bloembergen-Purcell-Pound model.     

Magnetic anisotropy and low-frequency dielectric response of weak ferromagnetic phase in κ-(BEDT-TTF)2Cu[N(CN)2]Cl, where BEDT-TTF is Bis(ethylenedithio)tetrathiafulvalene

We report a detailed characterization of the magnetism and AC transport in single crystals of the organic conductor -(BEDT-TTF)₂Cu[N(CN)₂]Cl by means of magnetic anisotropy measurements and low-frequency dielectric spectroscopy. Magnetic anisotropy obeys Curie-Weiss law with negative Curie-Weiss temperature in the temperature range 300 K-70 K. An antiferromagnetic transition with concomitant canted antiferromagnetic state is established at 22 K. A large hysteresis in the spin-flop transition and magnetic field reversal of the weak ferromagnetic magnetization are documented for the first time. A broad dielectric relaxation mode of moderate strength () emerges at 32 K, and weakens with temperature. The mean relaxation time, much larger than that expected for single-particle excitations, is thermally activated in a manner similar to the DC conductivity and saturates below 22 K. These features suggest the origin of the broad relaxation as an intrinsic property of the weak ferromagnetic ground state. We propose a charged domain wall in a random ferromagnetic domain structure as the relaxation entity. We argue that the observed features might be well described if Dzyaloshinsky-Moriya interaction is taken into account. A Debye relaxation with similar temperature dependence was also observed and seems to be related to an additional ferromagnetic-like, most probably, field-induced phase. We tentatively associate this phase, whose tiny contribution was sample dependent, with a Cu²⁺ magnetic subsystem. Received 15 June 1998 and Received in final form 1 February 1999     

KCl:OH中结构弛豫的红外发散响应

本文将红外发散响应理论应用到晶态KCl:OH中OH^-的取向变化弛豫过程,研究KCl:OH的低温超声吸收特性。结果表明T>4.5K时,超声吸收的主要贡献来自于热激活弛豫过程;T<4.5K时,超声吸收是热激活弛豫过程和隧道弛豫过程贡献的迭加。 关键词：     

Dielectric relaxation in liquid water: two fractions or two dynamics?

Dielectric relaxation in liquid water is studied using molecular dynamics (MD) simulations in the temperature range of 240 to 340?K at atmospheric pressure. The main dielectric and fast relaxation mode are identified in the spectra of dipole moment autocorrelation functions. The microscopic origin of the fast dielectric relaxation process, which takes place on a time scale of subpicoseconds at room temperature, is discussed. A new hypothesis for the fast dielectric mode is presented. It is based on the assumption of the intrawell rotational relaxation taking place during the waiting period between thermally activated large angle jumps occurring in the course of changing H-bond partners.     

石英中Al3+-空穴取向变化弛豫过程中的红外发散响应

基于α石英的晶体结构，将红外发散响应模型和双势阱模型应用到含Ａｌ杂质的α石英中Ａｌ³⁺－空穴的取向变化弛豫过程，研究其低温介电损耗特性，结果表明Ｔ＜６．５Ｋ时，介电损耗的主要贡献来自于单声子助隧道弛豫过程；Ｔ＞１０Ｋ时，主要贡献来自于热跃迁弛豫过程；而在中间温区，介电损耗是两种过程的迭加，同一弛豫体不同的弛豫过程对应于不同的红外发散响应，还讨论了同一弛豫体引起的超声弛豫损耗。 关键词：     

Electron spin-lattice relaxation rates for high-spin Fe(III) complexes in glassy solvents at temperatures between 6 and 298 K

The temperature dependence of spin-lattice relaxation rates was analyzed for four high-spin nonheme iron proteins between 5 and 20 K, for three high-spin iron porphyrins between 5 and 118 K, and for four high-spin heme proteins between 5 and 150 to 298 K. For the nonheme proteins the zero-field splittings, D, are less than 0.7 cm(-1), and the relaxation is dominated by the Orbach and Raman processes. For the iron porphyrins and heme proteins D is between 4 and 12 cm(-1) and the relaxation is dominated by the Orbach process between about 5 and 100 K and by a local mode at higher temperatures. The relaxation rates for the heme proteins in glassy matrices extrapolated to values at room temperature that are similar to values obtained by NMR relaxivity in fluid solution. This similarity suggests that for high-spin Fe(III) heme proteins with effective intramolecular spin-lattice relaxation processes, the additional motional freedom gained when a relatively large protein goes from glassy solid to liquid solution at room temperature has little impact on spin-lattice relaxation.     

Electron spin relaxation in pseudo-Jahn-Teller low-symmetry Cu(II) complexes in diaqua(L-aspartate)Zn(II).H(2)O crystals.

Low-temperature (4-55 K) pulsed EPR measurements were performed with the magnetic field directed along the z-axis of the g-factor of the low-symmetry octahedral complex [(63)Cu(L-aspartate)(2)(H2O)2] undergoing dynamic Jahn-Teller effect in diaqua(L-aspartate)Zn(II) hydrate single crystals. Spin-lattice relaxation time T(1) and phase memory time T(M) were determined by the electron spin echo (ESE) method. The relaxation rate 1/T(1) increases strongly over 5 decades in the temperature range 4-55 K. Various processes and mechanisms of T(1)-relaxation are discussed, and it is shown that the relaxation is governed mainly by Raman relaxation processes with the Debye temperature Theta(D)=204 K, with a detectable contribution from disorder in the doped Cu(2+) ions system below 12 K. An analytical approximation of the transport integral I(8) is given in temperature range T=0.025-10Theta(D) and applied for computer fitting procedures. Since the Jahn-Teller distorted configurations differ strongly in energy (delta(12)=240 cm(-1)), there is no influence of the classical vibronic dynamics mechanism on T(1). Dephasing of the ESE (phase relaxation) is governed by instantaneous diffusion and spectral diffusion below 20 K with resulting rigid lattice value 1/T(0)(M)=1.88 MHz. Above this temperature the relaxation rate 1/T(M) increases upon heating due to two mechanisms. The first is the phonon-controlled excitation to the first excited vibronic level of energy Delta=243 cm(-1), with subsequent tunneling to the neighbor potential well. This vibronic-type dynamics also produces a temperature-dependent broadening of lines in the ESEEM spectra. The second mechanism is produced by the spin-lattice relaxation. The increase in T(M) is described in terms of the spin packets forming inhomogeneously broadened EPR lines.     

蒽分子晶体的喇曼散射

在室温和液氮温度下,用氩离子激光器的5145Å激光激发,测量了蒽单品的喇曼散射谱,其喇曼活性主模振动的实验值和理论值符合的较好。计算了旋转振动的均方振幅,并对低波数振动喇曼谱的温度效应进行了讨论。     

重复频率脉冲大气放电中氮气的振动温度

氮气分子的振动自由度在大气放电低温等离子体中会被高度激发。从振动能级的简谐振子模型和Boltzmann分布近似出发,研究重复频率脉冲放电中振动温度的变化行为。结果表明,决定重频条件下振动温度的主要过程是电子碰撞振动激发和振动-平动弛豫,而在振动能级高度激发的情形下其与氧原子的化学反应也会产生影响。对于振动激发过程,通过跃迁反比相似率推导出的特征弛豫时间与动理学模型符合较好。在振动-平动弛豫中占主导贡献的为干燥大气中的氧原子或潮湿大气中的水分子。当氧原子数密度为1014 cm-3时,若初始振动温度在5000 K,在化学反应过程中振动能量的特征弛豫时间在0.1~1 s量级。     

MgB2超导薄膜的变温拉曼光谱研究

MgB₂作为迄今为止超导转变温度最高的合金超导体,由于其具有结构简单、相干长度长、晶界间不存在弱连接、上临界场很高、电-声散射时间短等特点,MgB₂超导薄膜在电子学领域有着广阔的的应用前景。拉曼光谱是研究电-声子相互作用和超导能带的一种有效方法,且已广泛用于分析MgB₂材料的电子、声子特征以及超导体能带结构,研究表明,样品质量、晶粒尺寸以及测试条件对MgB₂拉曼峰的峰位和峰形影响很大,其中拉曼光谱随温度的变化也是一个研究重点,但目前关于MgB₂变温拉曼光谱的研究,测试的温度范围相对较小,局限在83 K到室温区域或是转变温度附近。研究了大范围温度区间内MgB₂薄膜的拉曼光谱变化,采用混合物理化学沉积法在(0001)SiC衬底上制备了MgB₂多晶薄膜,薄膜的晶粒尺寸约为300 nm,超导转变温度为39.3 K,对其在10～293 K之间的拉曼光谱进行了测试,测量的波数范围为20～1 200 cm-1。变温拉曼光谱的测试结果显示,在高频620 cm-1附近以及低频80和110 cm-1附近存在MgB₂的拉曼峰。经分析,低频区域出现的两个拉曼峰的频率与超导能隙宽度相对应,表明MgB₂的双能隙特性。考虑到MgB₂中四种声子模式的拉曼活性,高频620 cm-1附近的拉曼峰应是由E_2g振动模所贡献的,且随着测试温度的降低,该拉曼峰的峰位未发生明显的偏移,但半高宽显著变小,从293 K时的380.7 cm-1减小到10 K时的155 .7 cm-1,分析表明E_2g声子与电子系统的非线性耦合所引起的非简谐效应可能是拉曼峰半高宽线性变小的主要原因。     

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。     

Impact of Chlorine Substitution on Spin–Lattice Relaxation of Triarylmethyl and 1,4-Benzosemiquinone Radicals in Glass-Forming Solvents Between 25 and 295 K

Spin–lattice relaxation rates measured by long-pulse saturation recovery in glassy solvents for chlorinated aromatic radicals: perchlorotriphenylmethyl radical, 2,5-dichloro-3,6-dihydroxy-1,4-benzosemiquinone, and tetrachloro-1,4-benzosemiquinone, were compared with relaxation rates for non-chlorinated analogs. The impact of the quadrupolar chlorines is small and less than the effects of changing the rigidity of the glass. The temperature dependence of relaxation rates below the glass transition temperature could be modeled as the sum of contributions from the direct, Raman, and local mode processes.     

Spin relaxation and ultra-slow Li motion in an aluminosilicate glass ceramic

The ion dynamics in a lithium aluminosilicate glass ceramic was studied using stimulated-echo 7Li-NMR. For temperatures 300 K相似文献   

Thermal properties of high-k Hf_1-xSi_xO₂

Classical atomistic simulations based on the lattice dynamics theory and the Born core-shell model are performed to systematically study the crystal structure and thermal properties of high-k Hf1-xSixO2 . The coefficients of thermal expansion, specific heat, Grneisen parameters, phonon densities of states and Debye temperatures are calculated at different temperatures and for different Si-doping concentrations. With the increase of the Si-doping concentration, the lattice constant decreases. At the same time, both the coefficient of thermal expansion and the specific heat at a constant volume of Hf1-xSixO2 also decreases. The Grneisen parameter is about 0.95 at temperatures less than 100 K. Compared with Si-doped HfO2 , pure HfO2 has a higher Debye temperature when the temperature is less than 25 K, while it has lower Debye temperature when the temperature is higher than 50 K. Some simulation results fit well with the experimental data. We expect that our results will be helpful for understanding the local lattice structure and thermal properties of Hf1-xSixO2 .     

Allene nu9 and nu10: Low-Temperature Measurements of Line Intensity

We report laboratory intensity measurements for the weak nu9 (998.8 cm-1) and intense nu10 (841.1 cm-1) bands of allene. Allene is predicted to be a constituent of Titan's atmosphere, and measurements of its abundance would yield important information about the atmospheric chemistry of that body. Spectra were obtained at a temperature of 200 K (approximating Titan conditions) using the high-resolution FTS instrument at Kitt-Peak National Observatory's McMath-Pierce observatory. A total of 505 nu9 and 687 nu10 line intensities were fit using a least-squares method to accurately determine two sets of transition dipole moments. Integrated band intensities computed utilizing the fitted parameters were found to be 36 +/- 4% cm-2 atm-1 and 301 +/- 4% cm-2 atm-1 for nu9 and nu10, respectively, at 200 K. Copyright 1999 Academic Press.     

Investigation of the creep and glass transition of elastomers by the microindentation method: Epoxy resin and related nanocomposites

The experimental procedure and theoretical grounds of the applicability of the microindentation method as one of the effective techniques of relaxation spectrometry of solid-state polymers have been developed. It has been shown that the glass transition temperature and rheological parameters of the material (unrelaxed and relaxed elastic moduli, strain viscosity coefficients) can be determined from measurements of the temperature dependence of the microhardness of polymers in a high-elasticity state and in the glass transition region with the recording of the long-term creep under the indenter. These measurements provide sufficient information for the formulation of a rheological model of the material under investigation. The results of these measurements are supplemented by the concepts of thermally activated motion of molecular segments as the microscopic mechanism of structural relaxation in polymers, which makes it possible to obtain empirical estimates for the activation energies and vibrational frequencies of the molecular segments. The method is implemented in experiments on the microindentation of the epoxy resin and its composites with the addition of carbon nanotubes in the temperature range 230–300 K. The glass transition of these polymers has been observed at temperatures near 260 K, the unrelaxed and relaxed Young’s moduli have been measured, and two thermally activated relaxation processes determining the glass transition, as well as the shortterm and long-term creeps of these materials (α- and α′-processes), have been revealed.     

13C NMR investigation of carbon nanotubes and derivatives

We report on nuclear magnetic resonance on single wall carbon nanotubes. Depending on the chemical preparation the electronic and dynamical properties of carbon nanotubes are presented and discussed. From a room temperature study of the spin lattice relaxation of carbon nanotubes prepared with various catalysts we clearly identified two components. In agreement with previous NMR studies and theoretical predictions, one-third of the intensity of the signal is found with a short relaxation time (about 5 s) attributed to metallic nanobutes while the rest of the signal presents a relaxation time of about 90 s corresponding to semiconducting nanotubes. In the case of oxidized or cut nanotubes only one relaxation time is observed with characteristics similar to the slow component. The disappearance of the fast relaxing component is associated with the absence of metallic nanotubes damaged by the chemical or mechanical treatments. In this case, the T dependence of the spin lattice relaxation reveals the effect of thermally activated small amplitude motions (twistons) of the nanotube in ropes. If diffusion of twistons might induce movement of ¹³C sites and local magnetic field fluctuations, orientational order could appear below the transition temperature of 170 K. In the last part, we present the theoretical predictions of chemical shift tensor in carbon nanotubes.     

Anomalous properties of new organic conductors: Comparison of bromanil,chloranil, and tetracyanoquinodimethane (TCNQ) salts of tetramethyltetrathiafulvalene (TMTTF)

Structural, conductivity, magnetic susceptibility, optical, infrared, and Raman data are reported for two new highly conducting organic solids, the bromanil and chloranil salts of TMTTF (tetramethyltetrathiafulvalene). These compounds are shown to have the two basic features essential to an organic metal: segregated stacks of planar, polarizable organic molecules and incomplete charge transfer. Nevertheless, their properties are strikingly different than, for example, those of the TMTTF salt of TCNQ (tetracyanoquinodimethane). The properties of the latter are typical of TCNQ-containing organic metals, with the conductivity and magnetic susceptibility $\text{both}$ becoming thermally activated below a (presumably) Peierls transition. In TMTTF-bromanil, on the other hand, the conductivity is already activated at room temperature, well above the transition (～75K) in the susceptibility. This behavior is not characteristic of a simple quasi-one-dimensional metal. Rather it indicates a magnetic semiconductor with appreciable Coulomb interactions, which undergoes a spin-Peierls-like transition at lower temperatures. The reason why the effects of Coulomb interactions are more dramatically manifested in these compounds is not understood.