时间分辨与偏振红外光谱研究电场诱导下手性反铁电液晶的翻转过程

手性反铁电液晶分子中的各个不同片段、不同基团在电场诱导下展现不同的取向与取向分布.在交变电场的作用下,分子中各个部分的翻转动力学行为也表现的不同.     

和频光谱研究萃取剂TOPO分子在空气/水界面处的取向行为

采用和频光谱研究了萃取剂TOPO分子在空气/水界面处的取向行为。研究发现,在不同膜压条件下,TOPO分子在水表面排布的有序化程度不同。膜压越大,TOPO分子在水表面的堆积密度越大,其分子碳链的取向越倾向于垂直空气/水界面。研究萃取剂分子在界面的取向行为,可以为理解界面处萃取剂分子与目标待萃取离子的相互作用机理提供思路。     

控制双激光脉冲的宽度提高N2分子的取向

提出了通过控制双激光脉冲宽度的方法来提高N2分子取向程度.利用数值方法求解了N2分子刚性转子模型在双激光脉冲作用下的薛定谔方程,计算了双原子分子N2在总强度固定的两束激光脉冲作用下.不同脉冲宽度对于N2分子取向的影响.研究结果表明,通过调整两束激光脉冲的宽度,选择合适的延迟时间能够有效提高N2分子的取向程度.     

从随机到取向--分子转动动力学的超快调控

分子取向物理是研究如何操控分子空间排列方向以及如何制备具有特定方向的分子。近十多年来,分子取向物理学取得巨大进展,人们通过各种技术对分子取向物理进行研究,使人们对分子取向的认识达到一个全新的高度。文章首先介绍了分子的量子态及其分布,转动量子态选择方法和分子的转动动力学,然后概述通过制备和调控转动态的相干布居来控制分子取向的方法。实验和理论表明,分子的不同转动态在相同激光条件作用下产生的转动波包不一样,从而导致分子的准直和取向程度随时间演化完全不一样。通过选择合适的转动量子态能够很好地提高分子取向程度。取向分子作为相互作用靶,为原子分子动力学、精密测量物理、立体化学反应和表面碰撞过程等提供了更加丰富多彩的研究内容。     

控制双激光脉冲的宽度提高N2分子的取向

提出了通过控制双激光脉冲宽度的方法来提高N₂分子取向程度. 利用数值方法求解了N₂分子刚性转子模型在双激光脉冲作用下的薛定谔方程，计算了双原子分子N₂在总强度固定的两束激光脉冲作用下，不同脉冲宽度对于N₂分子取向的影响. 研究结果表明，通过调整两束激光脉冲的宽度，选择合适的延迟时间能够有效提高N₂分子的取向程度. 关键词： 双激光脉冲 分子取向 脉冲宽度     

极化条件对偶氮化合物薄膜中分子取向的影响

 为探索不同的极化条件对分子取向的影响,用旋涂法制备了偶氮主客体掺杂薄膜,并用电晕极化的方法分别在不同温度和厚度条件下使分子取向,通过测量极化前后紫外-可见吸收谱,研究了平均取向因子的变化,并和二次谐波产生结果进行了比较。实验结果表明：对于厚度相同的偶氮薄膜,随着温度的升高,平均取向因子增大,但二次谐波信号强度先增大后减小;温度越接近聚合物玻璃转变温度,分子越容易取向,但温度过高,聚甲基丙烯酸甲酯变为粘滞态,部分偶氮分子容易在高温下蒸发掉,导致二次谐波信号强度降低,而平均取向因子增大;随着薄膜厚度的增大,针-板电极电场造成薄膜内部电场分布的不均匀性增加,极化效率降低,平均取向因子不断减小,二次谐波信号强度先增大后减小。     

菌紫质光致各向异性动力学的理论和实验

对菌紫质(Bacteriorhodopsin,BR)薄膜的光致各向异性特性进行了理论模拟.由随机取向的极性BR分子构成的聚合物薄膜在宏观上是各向同性的,但在线偏振光的作用下,BR分子对激发光的选择性吸收,导致不同异构体分子取向的不均匀分布,从而使BR薄膜在宏观上呈现出各向异性.利用BR光循环的二能级模型,得到了B态分子取向分布随时间的变化关系,推导出了BR薄膜光致各向异性动力学的数学表达式,模拟了不同激发光强下BR薄膜的光致各向异性动力学曲线,得到了和实验结果一致的计算结果.     

线性分子摆动光谱Q支相对强度与电场、分子取向度的依赖关系及其应用

提出了一种测量分子取向度的新方法,即采用极性线性分子的摆动光谱Q支相对强度来测量分子的取向度。通过计算极性分子HCN-N2电子基态的C—H伸缩振动在不同电场强度下的摆动光谱,发现其摆动光谱的Q支强度随着电场强度的增大而逐渐增大,但P支与R支强度则随着电场强度的增大相应地减小,因此可以利用摆动光谱的Q支相对强度(即Q支光谱强度与P,Q,R支光谱总强度的比值)来表示电场强度的大小。同时,计算了电场强度大小与分子取向度的关系,发现分子取向度随电场强度的增大而逐渐增大。通过进一步计算,给出了分子取向度与其摆动光谱的Q支相对强度的关系,并提出采用摆动光谱的Q支相对强度实现分子取向度测量的新方法。     

分子取向对CO在Pd(111)面吸附的影响

 用基于密度泛函理论广义梯度近似下的平面波赝势方法计算了在Pd(111)晶面两种不同CO分子取向的吸附结构。计算结果表明，CO分子碳端和氧端靠近Pd(111)面的吸附能分别为-1.75，-0.28 eV，碳端吸附的结构比氧端吸附能力强。因此，分子取向影响CO在Pd(111)面上的吸附，通过控制CO的取向可能减小Pd(111)的吸附进而减弱Pd(111)面CO分子的中毒。     

用另场微波技术对光激发三重态的研究

许多具有共轭双键和单基态的有机分子在光激发下转入到一个亚稳的最低的三重态,从此三重态回到基态产生磷光辐射和(或者)无辐射衰减。三重态的三个支能级对应于自旋角动量与分子构形的不同取向,这些取向对于分子内的磁场相互作用不完全一样,因此这三个支能级甚至在无外磁场时也多少具有不同的能量。这一另场分裂(ZFS)是分子中电子结构的特征,若用频率表示,其数量级为0.1-10GHz。     

Study of fast switching processes due to electric and magnetic fields-an NMR approach

Solid state NMR techniques have been developed to investigate dynamic molecular effects (e.g., molecular reorientations) due to simultaneously applied external electric fields on electrically sensitive materials such as liquid crystals (LC), liquid crystalline polymers (LCP) and polymeric electrets. Such effects can be observed only on relatively thin systems (10-200 μm). That means that many scans are necessary to achieve a sufficiently high signal-to-noise-ratio in the spectra (500-1000 scans). If the material is also magnetically sensitive, the electric field can be used to orient molecules in a starting orientational state and by switching-off the voltage to access fast reorientation processes in the magnetic field B₀. Until now, the behaviour of orientable molecular systems under the influence of electric fields has been investigated by means of a more or less quasistatic approach (LCP: 100 V, electrets: 1 kV) in equilibrium states. The achievable time resolution depends on the desired signal-to-noise-ratio. For the case of proton NMR this means a time resolution of about 10 min. However, very often switching processes occur on a much shorter time scale. Using conventional techniques it is impossible to observe fast (ca. 100 μs) electrically or magnetically induced reorientation processes. In this work, we present a concept to overcome the problems outlined above and to extend the area of our current in situ NMR investigations on thin electrically-switched or poled polymeric layers. The basic idea is to include synchronized electric pulses during the NMR experiment using the preparation and/or mixing periods of a 1D or 2D pulse sequence for the application of an orienting field (electric or magnetic) and to use the reversibility of the molecular switching phenomenon to achieve a sufficient signal-to-noise-ratio. The techniques extend the range of possible investigations from about 100 μs to approximately T₁ for correlated spectra (and to longer times of applied fields for uncorrelated spectra). Results are shown for a nematic LC and a nematic polymer having a similar side chain.     

In situ neutron diffraction studies of a commercial, soft lead zirconate titanate ceramic: response to electric fields and mechanical stress

Structural changes in commercial lead zirconate titanate (PZT) ceramics (EC-65) under the application of electric fields and mechanical stress were measured using neutron diffraction instruments at the Australian Nuclear Science and Technology Organisation (ANSTO) and the Oak Ridge National Laboratory (ORNL). The structural changes during electric-field application were measured on the WOMBAT beamline at ANSTO and include non-180° domain switching, lattice strains and field-induced phase transformations. Using time-resolved data acquisition capabilities, lattice strains were measured under cyclic electric fields at times as short as 30 μs. Structural changes including the (002) and (200) lattice strains and non-180° domain switching were measured during uniaxial mechanical compression on the NRSF2 instrument at ORNL. Contraction of the crystallographic polarization axis, (002), and reorientation of non-180° domains occur at lowest stresses, followed by (200) elastic strains at higher stresses.     

Freezing transition of interfacial water at room temperature under electric fields

The freezing of liquid water into ice was studied inside a gap of nanometer spacing under the control of electric fields and gap distance. The interfacial water underwent a sudden, reversible phase transition to ice in electric fields of 10(6) V m(-1) at room temperature. The critical field strength for the freezing transition was much weaker than that theoretically predicted for alignment of water dipoles and crystallization into polar cubic ice (>10(9) V m(-1)). This new type of freezing mechanism, occurring in weak electric fields and at room temperature, may have immediate implications for ice formation in diverse natural environments.     

基于密度泛函理论的外电场下双酚A型环氧树脂分子的结构及特性

采用密度泛函m062x的方法在6-31g(d)基组上对双酚A型环氧树脂分子进行优化得到了它的稳定结构,并且研究了不同外电场(0-0.013 a.u., 1 a.u.=5.142×10~(11) V/m)作用下双酚A型环氧树脂分子的分子结构、电偶极矩和分子总能量,偶极矩、极化率、前线轨道的能级和成分,原子之间的键能和红外光谱的变化.研究表明:随着外加电场的增大,双酚A型环氧树脂分子从倒V型结构逐渐变成线性结构,总能量降低,偶极矩和极化率都升高,且双酚A型环氧树脂分子的稳定性随着外加电场的增大而降低;最高占据轨道能级随着外加电场的增大而增大,沿逆电场方向分子链端表现出亲核反应活性,最低空轨道能级随着外加电场的增大而减小,沿电场方向分子链端表现出亲电反应;位于分子两端环氧基团上的C-C,C-O容易发生断裂,进而破环了双酚A型环氧树脂分子的稳定性;分子红外光谱在高频区的吸收峰出现了明显的红移现象.     

Observation of a pressure-induced first-order polyamorphic transition in a chalcogenide glass at ambient temperature

An apparently first-order polyamorphic transition has been observed with increasing pressure at ambient temperature in a molecular glass of composition Ge(2.5)As(51.25)S(46.25) Raman spectroscopic measurements on pressure-quenched samples and in situ x-ray diffraction measurements indicate that this transition corresponds to a collapse of the ambient-pressure molecular phase to a high-pressure network phase. The high-pressure phase first appears at a pressure of approximately 8-9 GPa and the transformation becomes complete at approximately 14-15 GPa. Calorimetric measurements indicate that the low- and high-pressure phases are thermodynamically distinct and that they coexist in the transition range.     

Supercooling molecular hydrogen down through the superfluid transition

Recent calculations by Vorobev and Malyshenko [JETP Lett. 71, 39 (2000)] show that molecular hydrogen may stay liquid and superfluid in strong electric fields of the order of 4x10(7) V/cm. I demonstrate that strong local electric fields of similar magnitude exist beneath a two-dimensional layer of electrons localized in the image potential above the surface of solid hydrogen. Even stronger local fields exist around charged particles (ions or electrons) if the surface or bulk of a solid hydrogen crystal is statically charged. Measurements of the frequency shift of the 1 --> 2 photoresonance transition in the spectrum of a two-dimensional layer of electrons above a positively or negatively charged solid hydrogen surface performed in the temperature range 7-13.8 K support the prediction of electric field induced surface melting. The range of surface charge density necessary to stabilize the liquid phase of molecular hydrogen at the temperature of superfluid transition is estimated.     

Dynamics of domain-wall motion in ferroelectric liquid crystals in an electric field

The director reorientation in smectic liquid crystals with ferroelectric properties has been considered in the case where the interaction of liquid-crystal molecules with the surface leads to a partial unwinding of the helical structure of the liquid crystal and the reorientation occurs as a result of the domain-wall motion. The dependences of the velocity of domain-wall motion on the electric field strength, electric field variation frequency, boundary conditions, spontaneous polarization, and viscosity of the liquid crystal have been determined. It has been demonstrated that an increase in the electric field variation frequency or the polar part of the anchoring energy and the spontaneous polarization of the liquid crystal at a constant field frequency results in an increase of the velocity of domain-wall motion. As a consequence, the time of the electro-optic response of the liquid crystal in weak electric fields (from 0.4 to 2.0 V/μm) decreases by a factor of more than three.     

Synchrotron x-ray study of the smectic layer directional instability

We have investigated the phenomenon of field-induced smectic layer instability, as monitored by synchrotron x-ray scattering. This instability means that, upon application of time-asymmetric electric fields to chiral smectics, the layer direction seems to "rotate" locally around an axis given by the direction of the applied field. For moderate values of field amplitude and asymmetry, domains with a favored layer inclination grow at the expense of unfavored ones, while larger fields and asymmetries generally lead to a chaotic flow behavior. At moderate amplitudes, we have followed the process of the horizontal layer folding (or horizontal chevron domain formation) and the smectic C* layer reorientation of ferroelectric liquid crystals by applying symmetric and asymmetric wave forms, respectively, and performing time resolved x-ray measurements. The studies unambiguously show the formation of a horizontal (in-plane, i.e., in a plane parallel to the cell substrates) chevron domain structure from a nonoriented sample by application of a symmetric electric field of sufficient amplitude. It is then demonstrated that a transition from the horizontal chevron domain structure to an in-plane uniform smectic layer direction takes place on application of asymmetric electric wave forms. Reversal of the field asymmetry reverses the inclination direction and selects the other layer normal direction as the uniform end state. The in-plane smectic layer reorientation process is followed here as it evolves, and analyzed directly by means of x-ray scattering.     

Improving Plasma Confinement by Controlling Hard X-Ray

Since runaway electrons and magnetohydrodynamics activity can contribute to serious damage and energy losses in tokamaks,the effect of an external electric field on runaway electrons and hard x-ray spectra is investigated.Parameters such as the plasma current,the hard x-ray photons count and the mean energy of runaway electrons are measured.Positive and negative voltages of 300 V are applied at 10 ms after the plasma initiation(while the plasma is forming),at 15ms(while the plasma is stable) and at 20ms(while the plasma is fading away) to attain the most effective time of applying the external electric held.The number of hard x-ray photons has the most changes in the range of 0-200 keV when the external electric fields are applied.Also in the duration of 20-30 ms of plasma the greatest number of hard x-ray spectra is detected.When the external electric fields are applied,the mean energy of runaway electrons reduces significantly,especially at 15ms(while the plasma is stable).     

Structural changes in block copolymers: coupling of electric field and mobile ions

We argue that the presence of dissociated ions in block copolymers under electric fields can induce strong morphological changes and even lead to phase transitions. We investigate, in particular, diblock copolymers in the body centered cubic (bcc) phase. In pure dielectric materials (no free charges), a dielectric breakdown is expected to occur for large enough electric fields, preempting any structural phase transition. On the other hand, dissociated ions are predicted to induce a phase transition to a hexagonal array of cylinders, at fields of about 10 V/microm or even lower. The strength of this mechanism can be tuned by controlling the amount of free ions present.