The effect of an anti-hydrogen bond on Fermi resonance:A Raman spectroscopic study of the Fermi doublet ν1-ν12 of liquid pyridine

The effects of an anti-hydrogen bond on the ν1-ν12 Fermi resonance(FR) of pyridine are experimentally investigated by using Raman scattering spectroscopy.Three systems,pyridine/water,pyridine/formamide,and pyridine/carbon tetrachloride,provide varying degrees of strength for the diluent-pyridine anti-hydrogen bond complex.Water forms a stronger anti-hydrogen bond with pyridine than with formamide,and in the case of adding non-polar solvent carbon tetrachloride,which is neither a hydrogen bond donor nor an acceptor and incapable of forming a hydrogen bond with pyridine,the intermolecular distance of pyridine will increase and the interaction of pyridine molecules will reduce.The dilution studies are performed on the three systems.Comparing with the values of the Fermi coupling coefficient W of the ring breathing mode ν1 and triangle mode ν12 of pyridine at different volume concentrations,which are calculated according to the Bertran equations,in three systems,we find that the solution with the strongest anti-hydrogen bond,water,shows the fastest change in the ν1-ν12 Fermi coupling coefficient W with the volume concentration varying,followed by the formamide and carbon tetrachloride solutions.These results suggest that the stronger anti-hydrogen bond-forming effect will cause a greater reduction in the strength of the ν1-ν12 FR of pyridine.According to the mechanism of the formation of an anti-hydrogen bond in the complexes and the FR theory,a qualitative explanation for the anti-hydrogen bond effect in reducing the strength of the ν1-ν12 FR of pyridine is given.     

Theoretical study of the relationship between the nearest-neighbor exchange coupling interactions and the number of peripheral complexes in the cyano-bridged CrMn6(CN)6 and CrMn2(CN)2 clusters

A theoretical density functional study of the relationship between the nearest-neighbor constants and the number of peripheral complexes in the cyano-bridged [Cr[CNMn(salen)(H2O)]6]3+ and [(5-Brsalen)2(H2O)2Mn2Cr(CN)6] clusters is presented. Two approaches show that the antiferromagnetic coupling interactions between nearest neighbors decrease with the increase of the number of peripheral complexes, although the second approach provides better results using several exchange-correlation functionals. The first approach consisted of evaluating the exchange coupling constant J(ij) between two paramagnetic metal centers i and j in the hexanuclear molecule by calculating the energy differences between the highest and broken-symmetry spin states of a model molecule in which metal atoms except for i and j are substituted by diamagnetic Zn(II) cations, while the second consisted of calculating the different spin-state energies of hexanuclear complexes and using the Heisenberg Hamiltonian to obtain the exchange coupling constants between different metal centers. Moreover, Kahn's qualitative theory succeeded in being applied to interpret the trend.     

磁场对滤纸上Zn电解沉积物形貌的影响

研究了外加磁场对滤纸上Zn分枝状电解沉积物生长形貌的影响.用金相显微镜和原子力显微镜观察Zn沉积物的显微结构.发现在非饱和浓度下生长的沉积物生长形貌受电解液浓度和滤纸纤维影响，外加磁场对其形貌的影响不明显.在饱和电解液浓度下获得的沉积物分枝分两层，并且贴近滤纸表面的薄层比其上面离滤纸较远的那一层生长快.在饱和浓度电解液情形下，0.40T外加磁场使得沉积物分枝发生明显的螺旋状偏转.在实验基础上结合相关理论，认为外加磁场通过霍尔效应影响滤纸上Zn分枝状电解沉积物形貌. 关键词： 电解沉积 磁场 霍尔效应 生长形态     

通量可控的双壁碳纳米管水分子泵

以双壁碳纳米管作为基本单元设计了一种新型纳米机械水泵, 其内管固定作为水分子通道, 外管做活塞式轴向运动. 分子动力学计算表明, 水分子净通量及管内水分子电偶极矩分布均与外管运动速率有强烈耦合效应. 该设计可以实现水分子的高效单向运输, 且输运效率可以通过外管活塞运动的速率进行调控. 这些发现可为未来实用纳米分子泵器件的设计提供新的思路.     

弱磁场对Zn分枝状电解沉积物形貌的影响

用金相显微镜和原子力显微镜分析了存在外加磁场情况下的Zn分枝状电解沉积物的微观形貌 ，并且根据实验结果提出了磁场使沉积物分枝呈现螺旋状偏转的机理.1)在沉积物晶粒的早 期生长阶段，当晶粒已经形成了择优生长方向但又非常小,仍然悬浮于电解液中时，磁流体 动力学对流作用于它上面的不平衡力使得晶粒连同它的择优生长方向向着对流下方偏转，直 到晶粒足够大，和它的前一个单晶枝晶连接在一起为止.2)当晶粒和它的前一个单晶枝晶连 接在一起以后，磁流体动力学对流的作用力已不足使它偏转.此时，如果电解液的浓度比较 高，单晶枝晶的一级分枝和二级分枝之间不存在对电解质的竞争关系，则此单晶枝晶将完全 按照初期形成的晶体择优生长方向直线生长，直到新的晶粒形核为止;如果电解液浓度较低 ，造成第一级分枝与第二级分枝的竞争关系，二级分枝总在第一级分枝的上游侧生长，使得 一级分枝向下游方向偏转.通过上述两个步骤，无论是枝晶沉积物还是分形沉积物都产生螺 旋状偏转. 关键词： 电解沉积 磁流体动力学对流 晶体择优生长方向 生长形态     

Exploring the sources of the magnetic anisotropy in a family of cyanide-bridged Ni9Mo6 and Ni9W6 systems: a density functional theory study

A density functional theory (DFT) study of the magnetic coupling interactions and magnetic anisotropy in a family of experimentally synthesized Ni(9)Mo(V) and Ni(9)W(V) systems is presented. Our calculations show that for all of our selected Ni(9)M(6) systems, the intramolecular magnetic coupling interactions are ferromagnetic, and the ground-state spins are 12. All of the D values of Ni(9)W(6) systems come mainly from the contribution of the D(i) of W(6)(CN)(48)Ni extracted from Ni(9)W(6), and the influence of the eight surrounding Ni including the ligands on their magnetic anisotropy is very small. Although the surrounding Ni bounded by different ligands have a small influence on all D values for our selected complexes, they decide on the core structures of W(6)(CN)(48)Ni, which dominate their magnetic anisotropy. Thus, to obtain a Ni(9)W(6) system having a large negative D, we can use different ligands bound to Ni to obtain a good core structure of W(6)(CN)(48)Ni with a large negative D value. All D values of Ni(9)Mo(6) systems also come mainly from the contribution of D(i) of the Mo(6)(CN)(48)Ni, which is positive or negative but very small; most of these systems do not behave as single-molecule magnets.     

HoVO4相变的高压拉曼光谱和理论计算研究

利用高温固相反应法制备了纯相的HoVO₄,并在0–21.25 GPa压强范围内测定了HoVO₄的拉曼光谱. 通过分析其拉曼峰的频移和劈裂变化情况,发现HoVO₄在9.3 GPa发生相变. 根据第一性原理选取并优化相似体系的高压晶体结构,将其与HoVO₄的常压锆石矿型I4₁/amd结构进行了能量比较,确认HoVO₄ 相变结构为白钨矿型结构（I4₁/a）. 研究结果表明,HoVO₄具有ScVO₄和YVO₄体系的从锆石矿型结构（I4₁/amd）至白钨矿型结构的相变过程. 分析对应结构相的体积随压强的变化,发现体积坍塌对该相变起重要作用. 上述研究结果有助于了解HoVO₄的高压结构以及该材料在高压特殊条件下的应用. 关键词： 锆石矿型结构 白钨矿型结构 拉曼光谱 第一性原理     

基于单Fabry-Perot标准具的双频率多普勒激光雷达数据反演技术

本文导出了大气后向散射信号光入射到Fabry-Perot (F-P)标准具的有效透过率表达式. 在基于单F-P 标准具的双频率多普勒激光雷达系统中, 采用平均值法定量分析了瑞利后向散射信号对风场测量准确度的影响. 提出了同时反演风速和后向散射比的非线性迭代方法, 并通过仿真试验验证了该方法的有效性. 同时, 导出了径向风速和后向散射比测量误差的具体表达式, 并据此进行了仿真. 仿真结果表明: 若假定望远镜接收到的总后向散射光子数为50000, 径向风速测量误差随后向散射比的增大迅速减小, 在±25 m/s的风速测量动态范围内, 当R_β > 1.2时, 误差小于3 m/s; 后向散射比测量误差随后向散射比的增大而增大, 与径向风速大小几乎无关, 当R_β<10时, 相对误差小于13%. 关键词： 多普勒激光雷达 Fabry-Perot标准具 边缘技术 双频率     

多重敏感性双亲共聚物P(DM-co-AA-co-CA)的自组装及性能

以甲基丙烯酸二甲胺乙酯（DM）、丙烯酸（AA）和香豆素丙烯酸酯化物（CA）为共聚单体,通过普通自由基溶液聚合合成了多重敏感性双亲共聚物P(DM-co-AA-co-CA),用傅里叶变换红外（FTIR）、核磁共振（1H-NMR）、凝胶渗透色谱（GPC）和差示扫描量热仪（DSC）对聚合物结构进行表征．在选择性溶剂四氢呋喃/水中对所得多重敏感性双亲共聚物P(DM-co-AA-co-CA)进行自组装,结果表明,调节组装环境的pH值可以得到荷正电或负电的两性胶束粒子．用紫外可见光分光光度计、荧光分光光度计、Zeta电位测定仪、DLS和TEM研究了多重敏感性双亲共聚物的溶液自组装及其组装体的性能,结果显示,调节pH值可以有效的控制胶束的粒径大小及其LCST,并在pH为8.54时胶束溶液的紫外吸收和荧光发射强度达到最大值,且该胶束溶液在酸碱性较强时具有良好的乳化性能．     

Study of second-order nonlinear hyperpolarisability of all-trans-β-carotene in solutions by linear spectroscopic technique

This paper demonstrates the second-order nonlinear hyperpolarisability \gamma of all-trans-β-carotene in different solvents by linear spectroscopic technique that is based on resonance Raman scattering and UV--VIS (Ultraviolet-visible) absorption spectroscopy. Owing to the two-level model well describing the link that exists between the resonance Raman scattering and stimulated Raman scattering, the stimulated Raman polarisability α_{\rm R} can be calculated through the two-photon resonance system. The value of \gamma of all-trans-β-carotene in carbon bisulfide solution is 6.435\times 10^{-33} esu (1~esu of resistance =8.98755\times10^{11}~\Omega) that is close to the true value, because the solution of all-trans-β-carotene in carbon bisulfide satisfies the rigid resonance Raman scattering condition. This method is expected to be worthy of applications to measure the second-order nonlinear hyperpolarisability of a conjugate organic molecule.