核磁方法研究离子液体与丙酮的相互作用

运用核磁共振手段, 研究了室温离子液体1-辛基-3-甲基咪唑四氟硼酸盐([C8mim][BF4])在不同比例的离子液体／丙酮混合体系中1H和13C的化学位移及13C的自旋-晶格弛豫时间(T1). 结果表明, 离子液体[C8mim][BF4]的阳离子芳环上的氢原子, 以及与氮原子直接相连的甲基和亚甲基上的氢原子都与丙酮羰基上的氧原子有相互作用, 从而减弱了离子液体阴阳离子间的强相互作用, 使离子液体的运动加快, 黏度降低.     

卡宾单重态与乙烯环加成反应中的轨道作用图象

卡宾单重态与乙烯环加成反应已有很多计算工作和轨道作用的解释。由于该反应的C_(2v),对称性反应道的反应为禁阻反应,故反应取先由分子平面互相平行而后转向互相垂直的C_s对称性反应道。本文拟就这个反应过程中前线轨道的相互作用及变化情况提出一个简化模型,以期得到对全过程的清晰面象。1.正则轨道图象:     

Diatomic interaction energies in the topological theory of atoms in molecules

Summary A partitioning of theab initio total energy into one-center and two-center terms is proposed. The partitioning scheme is developed using the auxiliary function (2, 1; 1, 2) = γ(2, 1)γ(1, 2) and the topological theory of atoms in molecules. It is shown that this scheme can be used at theoretical levels beyond Hartree-Fock. The numerical results indicate that the two-center terms follow the experimental trend of the dissociation energies for a series of related compounds.     

Origin of the Landau-Lifshitz hydrodynamic fluctuations in nonequilibrium systems and a new method for reducing the Boltzmann equation

The Landau-Lifshitz fluctuating fluxes in fluctuating hydrodynamics are derived from the deterministic Boltzmann equation with the aid of a reduction method developed by Fujisaka and Mori. Thus it is shown that the hydrodynamic fluctuations innonequilibrium systems are generated by the reduction of variables from the-space distribution function to its five momentum moments, i.e., the hydrodynamic variables. This differs from the Bixon-Zwanzig and Fox-Uhlenbeck theories, in which the Landau-Lifshitz fluctuating fluxes are derived from the molecular fluctuating force in thestochastic Boltzmann-Langevin equation, which is, however, negligible in nonequilibrium systems. Thus the present method improves the Chapman-Enskog reduction method so as to include the hydrodynamic fluctuations generated by the reduction of variables.Supported in part by the Scientific Research Fund of the Ministry of Education.     

Fe–Hg Interactions and P Chemical Shifts in [Fe(CO)3 (PPh2R)2(HgCl2)] (R=pym, fur, py, thi)

In order to study the effects of R group on Fe–Hg interactions and 31P chemical shifts, the structures of mononuclear complexes Fe(CO)₃(PPh₂R)₂ (R=pym:1, fur: 2, py: 3,thi: 4; pym=pyrimidine, fur=furyl, py=pyridine, thi=thiazole) and binuclear complexes [Fe(CO)₃(PPh₂R)₂(HgCl₂)] (R=pym: 5, fur: 6, py: 7, thi: 8) were studied using the density functional theory (DFT) PBE0 method. The 31P chemical shifts were calculated by PBE0-GIAO method. Nature bond orbital (NBO) analyses were also performed to explain the nature of the Fe–Hg interactions. The conclusions can be drawn as follows: (1) The complexes with nitrogen donor atoms are more stable than those with O or S atoms. The more N atoms there are, the higher is the stabilility of the complex. (2) The Fe–Hg interactions play a dominant role in the stabilities of the complexes. In 5 or 6, thereisa σ-bond between Fe and Hg atoms. However, in 7 and 8, the Fe–Hg interactions act as σ_P–Fe→n_Hg and σ_C–Fe→n_Hg delocalization. (3) Through Fe→Hg interactions, there is charge transfer from R groups towards the P, Fe, and Hg atoms, which increases the electron density on P nucleus in binuclear complexes. As a result, compared with their mononuclear complexes, the 31P chemical shifts in binuclear complexes show some reduction.     

低于300℃时两种氧化铈材料对稀燃阶段NOx存储性能的影响

研究了低于300 ℃时两种氧化铈对稀燃阶段NO_x存储性能的影响,催化剂由2%（w）Pt/Al₂O₃（PA）与CeO₂-X（X=S,I）机械混合制备. X射线衍射（XRD）,BET表面积和扫描电子显微镜（SEM）用于表征材料的物理结构. X射线光电子能谱（XPS）和H₂程序升温还原（H₂-TPR）用于表面Ce³⁺和活性氧定量. 原位漫反射傅里叶变换红外光谱（in-situ DRIFTS）用于分析表面NO_x吸附物种. 相比于CeO₂-I,CeO₂-S 具有优良的物理化学性能,包括高比表面积、丰富的空隙结构、较高的抗老化能力及表面Ce³⁺浓度. 因而,Pt/Al₂O₃+CeO₂-S 表现出优异的NO_x存储能力. 此外,PA+CeO₂-X（X=S,I）上存在Pt 与CeO₂之间的相互作用,可提高表面氧物种的活性进而促进NO氧化及NO_x存储. PA+CeO₂-S上的这种相互作用要强于PA+CeO₂-I. 研究表明,表面Ce³⁺浓度和活性氧含量对NO_x存储起到重要作用. 然而经过水热处理后,Pt 与老化的氧化铈（ACS,ACI）之间的相互作用降低,并且两种氧化铈NO_x存储性能显著下降. 另外,与PA+ACS（ACI）相比,PA+PACS（PACI）样品NO_x存储能力得到改善,这归因于表面氧物种活性增加能促进硝酸盐的形成.     

Attractive halogen–halogen interactions: F3CCl⋯FH and F3CCl⋯FCH3 dimers

The F₃CCl?FH and F₃CCl?FCH₃ dimers, which feature the halogen–halogen contacts, are investigated at MP2/6–311++G(d,p) and MP2/aug–cc–pVDZ levels of approximation. The binding energies of these complexes are found to be comparable to those of the weak hydrogen bonds. In both complexes the Cl?F are found to be significantly shorter than the sum of the corresponding van der Waals radii. The C–Cl?F contacts are also found to exhibit certain deviation from linearity. However, the energy differences between linear and bent structures are very small and primarily accounted for by electrostatic interactions between remote parts of the dimer. This indicates a high conformational flexibility of the halogen–halogen contacts and may help to explain the diversity of structural features in crystals formed by halogen-containing molecules. In both dimers the halogen–halogen interaction leads to certain shortening of the C–Cl electron accepting bond. This is accompanied by a small increase of the C–Cl stretching frequency. Hence, the two investigated dimers can possibly be classified as the blue-shifting halogen–halogen contacts.     

Colloidal forces between bitumen surfaces in aqueous solutions measured with atomic force microscope

Colloidal forces between bitumen surfaces in aqueous solutions were measured with an atomic force microscope (AFM). The results showed a significant impact of solution pH, salinity, calcium and montmorillonite clay addition on both long-range (non-contact) and adhesion (pull-off) forces. Weaker long-range repulsive forces were observed under conditions of lower solution pH, higher salinity and higher calcium concentration. Lower solution pH, salinity and calcium concentration resulted in a stronger adhesion forces. The addition of montmorillonite clays increased long-range repulsive forces and decreased adhesion forces, particularly when co-added with calcium ions. The measured force profiles were fitted with extended DLVO theory to show the repulsive electrostatic double layer and attractive hydrophobic forces being the dominant components in the long-range forces between the bitumen surfaces. At a very short separation distance (less than 4–6 nm), a strong repulsion of steric origin was observed. The findings provide a fundamental understanding of bitumen emulsion stability and a mechanism of bitumen “aeration” in bitumen recovery processes from oil sands.     

On the equation of state of classical one-component systems with long-range forces

Several definitions of the pressure are introduced for one-component systems and shown to be nonequivalent in the presence of a rigid neutralizing background. Relations between these pressures are derived for finite and infinite systems; these relations depend on the asymptotic behavior of the force at infinity, with the Coulomb force at the borderline between different properties. It is argued that only one of those definitions is physically acceptable and its properties are discussed in relation to the asymptotic behavior of the force. It is seen in particular that a knowledge of the state of the infinite system is not sufficient to determine its thermodynamic properties. The results are illustrated by some typical examples.For example, for two-dimensional systems with three-dimensional Coulomb interaction see refs. 2–4.     

π-CONJUGATED OLIGOMERS IN SUPRAMOLECULAR CRYSTALS AND THEIR OPTOELECTRONIC FUNCTIONS

Functional organic molecular materials and conjugated oligomers or polymers now allow the low-cost fabrication of thin films for insertion into new generations of electronic and optoelectronic devices. The performance of these devices relies on the understanding and optimization of several complementary processes. Our goal is to discuss the relationship between the molecular stacking structures and their optoelectronic properties that are of importance in all these areas. The concept of intermolecular interaction should be taken here in the special sense that is inter-dipole coupling. Specifically, we will address the impact of inter-dipole interaction between adjacent molecules in aggregate state on the solid-state emission properties.