C60分子在有序-无序和玻璃态相变间的取向概率与弛豫行为

用极限动力学模型研究了C60分子在有序-无序相变和玻璃态相变温度区间取向角为98°和38°的取向概率与温度的关系.计算结果在玻璃态相变点附近的85!K,90!K和有序-无序相变点的260!K分别与实验值相吻合,取向概率对实验值更精确的拟合及其对温度的二阶导数预言玻璃态相变点在84!K.导出了弛豫规律,其结果表明:双能级的C60分子从非平衡态到平衡态的弛豫行为与非指数因子β有关,其总的弛豫时间决定于其中一个较短的弛豫时间,展宽指数形式保持不变.讨论了KWW方程的非指数因子β与分子间协同作用的关系,发现与双取向态间的能级差有关,计算值与实验结果相同.     

K3C60在200K附近的取向相变机理

研究了K₃C₆₀单晶薄膜在200K附近的导带结构.样品温度为190K时,同步辐射角分辨光电子谱能够观察到[111]方向有规律的能带色散.而在220K附近色散不存在.这一实验结果与K₃C₆₀在200K存在取向相变相符合.用反铁磁Ising模型对实验结果进行了分析.结果表明,K₃C₆₀在200K的相变是由低温下的一维无序取向结构转变为200K以上的双取向结构畴与无序分子(约占40 关键词： 3C₆₀')" href="#">K₃C₆₀ 取向相变机理     

铁电体中极化长程涨落的光子关联谱实验研究

从极化团簇的随机涨落出发, 利用维纳过程模型, 推导了铁电体中极化长程涨落的弛豫规律以及光强自相关函数所可能的表现形式. 阐述了微观极化团簇的弛豫过程与宏观测量弛豫规律之间的联系. 通过对原有氦氖激光光子关联谱实验装置进行改进, 观测了BaTiO₃和0.71Pb(Mg_1/3Nb_2/3)O₃-0.29PbTiO₃单晶中极化团簇长程涨落在居里点和立方到四方相变点附近的弛豫过程. 在BaTiO₃中发现极化团簇长程涨落在居里点之上4 K存在双弛豫现象, 此现象与其有序无序相变机理相联系. 在Pb(Mg_1/3Nb_2/3)O₃-0.29PbTiO₃中发现极化团簇长程涨落在相变点两侧都存在双弛豫现象. 利用推导的理论结果很好地拟合了实验结果并提取了极化团簇长程涨落的弛豫时间. 两种样品中极化团簇长程涨落的弛豫时间都在相变点出现突变, 并呈现临界慢化现象.     

电子关联对C60激子极化子的影响

本文采用扩展的Ｈｕｂｂａｒｄ模型，在电子－晶格耦合的紧束缚近似下，研究了光激发下的Ｃ₆₀，分子的激子态和极化子态。我们发现，电子关联效应相当敏感地影响到单态和三态激子的束缚能。同时，Ｃ₆₀分子动力学晶格弛豫使激子极化子得以形成。光激发下的Ｃ₆₀分子，在电子相互作用Ｕ～５．０ｅＶ，Ｖ～２．０ｅＶ时，能够定性地解释荧光发射谱。 关键词：     

C60晶体在有序相的分子取向结构

以C60 晶体中分子两种取向排列形成的双能级系统为基础 ,通过探讨C60 晶体在有序相的热力学性质 ,得到了 38o 和 98o 两种取向排列的分子在晶体中均匀分布的结构稳定性结论 .根据已报道的C60 晶体在有序相两端点温度 85K和 2 6 0K取向分布的实验结果 ,将较高的分子取向 (38o)能级的概率转化成分数值 1/ 6和 3/ 8,得到了有序相两种取向分子在两温度端点的分布规律 .当概率的分数值为 1/ 4和 1/ 3时 ,C60 晶体将具有较大的结构稳定性和较小的介电损耗及内耗值 ,对应的温度分别为 12 2 .6和 194 .3K .因而解释了介电实验结果出现异常的现象是由 38o 取向分子均匀分布的“规则 无规 规则”变化所造成的 .     

CCl4,CH2Cl2和CHCl3对磷脂酰胆碱紫外电子吸收光谱的影响

测量了ＣＣｌ₄，ＣＨ₂Ｃｌ₂和ＣＨＣｌ₃对生物膜中磷脂酰胆碱作用的紫外电子吸收光谱，实验结果表明，由于ＣＣｌ₄，ＣＨ₂Ｃｌ₂和ＣＨＣｌ₃分子结构的差异，三种溶剂的极性依次递增，磷脂酰胆碱π－π^*电子跃迁的吸收峰红移。磷脂酰胆碱在ＣＣｌ₄中光谱呈单吸收峰，在ＣＨ₂Ｃｌ₂和ＣＨＣｌ₃中光谱特征呈双蜂结构，存在聚集体的激子态跃迁，由此给出了脂质分子聚集状态的光谱依据。 关键词：     

基于激发态吸收的C60分子全光开关特性研究

用５３２．０ｎｍ的脉冲Ｎｄ：ＹＡＧ激光作为泵浦光，７４７．０ｎｍ的连续半导体激光作为探测光，在Ｃ₆₀甲苯溶液中，利用Ｃ₆₀分子的三重态－三重态非线性吸收效应，获得Ｃ₆₀分子的全光开关和全光调制特性，并用速率方程进行了动力学数值模拟，得到与实验相一致的结果。 关键词：     

C60分子晶体中的类非晶散射研究

根据Ｘ射线衍射基本理论，计算了Ｃ₆₀分子晶体中的各种堆积方式下的Ｘ射线衍射花样，对Ｃ₆₀分子晶体中的类非晶散射产生的原因进行了探讨，指出在Ｃ₆₀分子晶体中，Ｃ₆₀分子有两种运动方式．非晶散射是Ｃ₆₀分子晶体固有结构特征所造成的 关键词：     

在辐射阻尼存在下有效横向弛豫时间T*2的快速测定

利用CPMG自旋回波技术,通过一连串180°脉冲抑制辐射阻尼效应,让磁化矢量经过横向弛豫T₂过程大幅度衰减后再检测回波信号的线宽,该方法可直接获得有效横向弛豫时间T*₂,并可在CPMG测试T₂值的同时进行. 另外,当饱和恢复法用于估计T*₂值时,信号检测必须使用小角度脉冲.所有结果已进行了实验验证.     

时间和空间无序对玻璃超声弛豫的影响——红外发散响应理论的推广

本文采用时间连续无规行走(CTRW)的分形理论(Fractal),讨论玻璃超声弛豫过程中时间和空间无序对缺陷态激发寿命几率分布和特征弛豫时间的影响,并由此修正红外发散响应(IDR)理论,使其可能解释金属玻璃态超声弛豫现象。 关键词：     

ELECTRICAL PROPERTIES, EQUATIONS OF STATE AND PHASE TRANSITION IN SOLID C60 AT HIGH PRESSURE

Electrical properties and equations of state in solid C₆₀ at room temperature and high pressure have been studied in a diamond anvil cell using capacitance and resistance measurements and a piston-cylinder type device using P-V measurements, respectively. Experimental results by capacitance and P-V measurements indicate that solid C₆₀ also undergoes a phase transition at room temperature and a lower pressure, about 2GPa. The phase transition may be from a face-centered-cubic to a simple-cubic structure.     

Molecular dynamics study of orientational melting and thermodynamic properties of C<Subscript>60</Subscript>@C<Subscript>240</Subscript> nanoparticles

The barriers to relative shell rotation and other energy characteristics of C₆₀@C₂₄₀ two-shell carbon nanoparticles (“onions”) with outer shells of different shapes are calculated. The disturbance of the orientational order in the mutual arrangement of shells with an increase in temperature (orientational melting) is studied by the molecular dynamics method. The intershell orientational diffusion is represented by the Arrhenius relationship, and the Arrhenius parameters are calculated numerically. A definition is proposed for the temperature of short-range order disturbance in systems that undergo melting without structural change. The calculated temperature of orientational melting of the C₆₀@C₂₄₀ nanoparticle is approximately equal to 60 K.     

Study of the orientation of HNO3 molecules intercalated in graphite using nuclear techniques

Nuclear resonance scattering of photons from ¹⁵N has been used to study the orientation of the HNO₃ intercalant molecule with respect to the graphite planes. In the second-stage compound C₁₀(HNO₃) and the temperature range T = 15°K ? 300°, no orientational phase transition was observed and the NO₃ molecular plane was found to be oriented at an angle θ ∽ 82 ± 8° with respect to the graphite planes.     

Temperature dependence of elastic moduli for solid C60

The attenuation and velocity of ultrasonic waves (at a frequency of ～4 MHz) along the 〈111〉 and 〈100〉 directions in solid C₆₀ single-crystal samples are measured in the temperature range 100–300 K. The temperature dependences of the complete set of elastic constants for C₆₀ fullerite are determined from the experimental data. It is shown that the specific features in the behavior of the elastic moduli near the orientational phase transition temperature are associated with different contributions of the relaxation processes to the effective elastic moduli. The activation volume and deformation potentials for the ground and excited states of the C₆₀ low-temperature phase are evaluated from the results obtained in this work and the data available in the literature.     

Relaxation contribution to shear moduli of the low-temperature phase of solid C60

The relaxation contribution of the molecular reorientation in an elastic field of an acoustic wave to the effective shear moduli is calculated in the framework of the phenomenological two-level model of orientational states in the low-temperature phase of solid C₆₀. The polarity of the rotation axis of C₆₀ molecules and the possible existence of orientational domains in the structure of the low-temperature phase are taken into consideration. The estimates obtained are compared with the available experimental data.     

QUANTUM EFFICIENCY AND MULTIPHONON NONRADIATIVE TRANSITION OF Er3+ IONS IN FLUORIDE GLASS

Optical absorption, emission and excitation spectra, lifetimes of ⁴S_3/2 state and ⁴F_9/2 state from 10K to 500K, and Raman spectra were measured for Er³⁺ ions in fluoride glass. The radiative transition probabilities were calculated on the basis of Judd-Ofelt theory. The nonradiative transition probabilities and the quantum efficiencies were determined by calculating the difference between the measured lifetimes and the calculated radiative transition probabilities. The temperature dependence of nonradiative transition provavility was investigated using the Huang-Rhys theory of multiphonon relaxation , in which two kinds of phonons as well as the parameter s were taken into consideration. A fairly good agreement of the theoretical calculation with the experimental results has been obtained. The value of s is estimated and the effect of s is discussed.     

Ab initio potential energy surface and intermolecular vibrational frequencies of C3–Ar complex

The intermolecular potential energy surfaces for C₃–Ar have been calculated by supermolecular CCSD(T) and MP4 methods. The MP4 and CCSD(T) potentials have similar global behaviours. Their global minima all correspond to the slightly distorted T-shaped geometries. From these two potentials, the intermolecular vibrational energies and wavefunctions were calculated. The energy level patterns of the vdW vibrational states were predicted for the C₃–Ar complex. The zero point bending motion of this complex has a range of approximately 60°. The calculated transition frequencies of vdW bending agree well with available experimental data.     

Ordering phenomena in C<Subscript>60</Subscript>-tetraphenylphosphonium bromide

The fulleride salt C₆₀-tetraphenylphosphonium bromide is investigated as a function of temperature by single crystal X-ray diffuse scattering and diffraction. At room temperature, the C₆₀ orientational disorder is found to be more complex than previously expected. Moreover, a structural phase transition, due to the C₆₀ orientational ordering, is evidenced around 120 K. Its relation with the stabilization of a static Jahn-Teller effect is discussed. Received 3 November 1999     

Parameters of LC molecules’ movement measured by dielectric spectroscopy in wide temperature range

Dielectric properties of a nematic liquid crystal (NLC) mixture ZhK-1282 were investigated in the frequency range of 10²–10⁶Hz and a temperature range of ?20 to 80?°С. On the basis of the Debye’s relaxation polarization model dielectric spectra of temperature dependence of the orientational relaxation time τ and the dielectric strength δe were numerically approximated at the parallel orientation of a molecular director relative to alternating electric field. Influence of ester components in the mixture plays crucial role in relaxation processes at low temperature and external field frequency. The activation energy of the relaxation process of a rotation of molecules around their short axis was measured in a temperature interval of ?20 to ?+15?°С in which the dispersion of a longitudinal component of the dielectric constant takes place. The energy of potential barrier for polar molecules rotation in the mesophase was calculated. The value of the transition entropy from the nematic to isotropic phase was obtained from this calculation. The values of the coefficient of molecular friction and rotational diffusion were obtained by different methods. The experimental data obtained are in a satisfactory agreement with the existing theoretical models.