Ab initio global potential-energy surface for H5(+) --> H3(+) + H2

An accurate global potential-energy surface (PES) is reported for H5(+) based on more than 100,000 CCSD(T)/aug-cc-pVTZ ab initio energies. This PES has full permutational symmetry with respect to interchange of H atoms and dissociates to H3(+) and H2. Ten known stationary points of H5(+) are characterized and compared to previous ab initio calculations. Quantum diffusion Monte Carlo calculations are performed on the PES to obtain the zero-point energy of H5(+) and the anharmonic dissociation energy (D0) of H5(+) --> H3(+) + H2. The rigorous zero-point state of H4D+ is also calculated and discussed within the context of a strictly classical approach to obtain the branching ratio of the reaction H4D+ --> H3(+) + HD and H2D+ + H2. Such an approach is taken using the PES and critiqued based on the properties of the quantum zero-point state. Finally, a simple procedure for adding the long range-interaction energy is described.     

Light emission from chlorine atoms formed in the dissociative excitation of HCI in a flowing afterglow of discharged argon

Light emission from Cl(5p) atoms (near 440 nm) produced in the reaction of HCl in a discharged flow of argon was investigated with a flowing-afterglow apparatus. Ionic species, most probably argon ions in metastable states, Ar^+M, were found to be responsible for the Cl(5p) production in the dissociative excitation of HCl.     

Molecular structures of isobutene and 2,3-dimethyl-2-butene as studied by gas electron diffraction

The structures of isobutene and 2,3-dimethyl-2-butene have been studied by gas electron diffraction. For isobutene the rotational constants obtained by Laurie by microwave spectroscopy have also been taken into account. Leastsquares analyses have given the following r_g bond distances and valence angles (r_av for isobutene and r_α for dimethylbutene): for isobutene, r(CC) = 1.342±0.003 Å, r(C-C)= 1.508±0.002Å, r(C-H, methyl) = 1.119±0.007 Å, r(C-H, methylene) = 1.095±0.020 Å, ∠(C-CC) = 122.2±0.2°, ∠(H-C-H) = 107.9±0.8°, and ∠(C-C-H) 121.3±1.5°; for dimethylbutene, r(CC)= 1.353 ±0.004 Å, r(C-C) = 1.511±0.002 Å, r(C-H) = 1.118± 0.004 Å, ∠(C-CC)= 123.9±0.5°, and ∠(H-C-H)= 107.0±1.0°, where the uncertainties represent estimated limits of experimental error. The bond distances and valence angles in these molecules and in related molecules are compared with one another. The CC and C-C bond distances increase almost regularly with the number of methyl groups, and the C-C bonds in isobutene and dimethylbutene are shorter than those in acetaldehyde and acetone by about 0.01 Å. Systematic variations in the C-CC angles suggest the steric influence of methyl groups.     

Molecular structure of 1,1-difluoroethylene as determined by gas phase electron diffraction and microwave data

The structure of 1,1-difluoroethylene was determined, from gas phase electron diffraction data obtained independently in Leiden and Tokyo and the rotational constants of F₂CCH₂, F₂CCHD and F₂CCD₂ derived from the microwave study by Chauffoureaux. The two electron diffraction data agreed without significant discrepancy. From a joint least squares analysis of the diffraction and microwave data, the following r_g bond distances and r_z bond angles were derived: CC = 1.340 ± 0.006 Å, C-F = 1.315 ± 0.003 Å, C-H = 1.091 ± 0.010 Å, ∠C-C-F = 124.7 ± 0.3°, ∠C-C-H = 119.0 ± 0.4°, where the uncertainties represent estimated limits of error.     

Stannous oxalate as a novel catalyst for the synthesis of polytrimethylene terephthalate

Stannous oxalate was prepared efficiently and characterized by XRD and FT-IR. It exhibited higher catalytic activity and had profitable effect than tetrabutyl titanate and stannous octoate for the synthesis of polytrimethylene terephthalate (PTT) via esterification-route. Over this catalyst, the degree of esterification of pure terephthalic acid was up to 94.4% at 260°C after 1.5 h, while the intrinsic viscosity and content of terminal carboxyl groups of the corresponding PTT polyester, polymerized at 260°C, 60 Pa for 2 h, was 0.8950 dL/g and 15 mol/t, respectively. Stannous oxalate was a promising catalyst for the synthesis of PTT polyester.     

有机阳离子[C18mim]＋在蒙脱土层间的物理化学吸附与聚集状态*

咪唑基离子液体(N鄄十八烷基鄄N忆鄄甲基溴化咪唑盐[C18mim]Br)中的[C18mim]+可以通过离子交换反应进入蒙脱土层间.本文用TGA、FTIR和XRD 研究了[C18mim]+在蒙脱土层间的物理和化学吸附及其聚集状态. 研究结果表明, 蒙脱土存在着饱和的化学吸附量, 其总吸附量随物理吸附量的增加而增加；随着[C18mim]+在蒙脱土层间吸附量的增加, 其聚集态结构的有序性增加, 并伴有分子链的构象变化,导致层间距的增加.     

CeO2和Pd在Ni/γ-Al2O3催化剂中的助剂作用

采用脉冲微反技术研究了添加n型半导体氧化物CeO2及贵金属Pd对Ni/γ Al2O3催化剂上CH4积炭/CO2消炭反应性能的影响,并运用BET、TPR、CO2 TPSR及氢吸附等技术对催化剂进行了表征.结果表明, n型半导体氧化物CeO2的添加可以降低Ni/γ Al2O3催化剂上CH4裂解积炭活性,提高CO2消炭活性,添加少量贵金属Pd可以进一步改变载体Al2O3、助剂CeO2和活性组分Ni之间的相互作用,从而改善Ni/γ Al2O3催化剂的抗积炭性能.通过Ni Ce Pd/γ Al2O3催化剂上CH4积炭/CO2消炭模型对上述作用机制作出了新的解释.     

新型镍催化剂催化乙烯聚合的阳离子机理

含氮氧配位原子的镍催化剂是一类新型催化剂.文章以配体为[NH=CH－CH=CH－O]的镍催化剂为模型,用密度泛函方法（DFT）在B3LYP/LANL2MB水平上研究了该类乙烯聚合催化的反应机理.计算结果表明,催化的反应过程中,中心原子镍最先形成带空位的四边形阳离子配合物,乙烯以垂直于催化剂平面的方式占据空位,然后旋转到催化剂平面内以利于插入反应的进行；插入反应发生后,在催化剂中Ni和β-C之间形成一种氢桥键,协助新空位的形成,实现链的增长.     

6-甲氧基-2-丙酰基萘在醇溶剂中的溴化反应

室温下，6－甲氧基－2－丙酰基萘和1，3－二溴－5，5－二甲基海因的溴化反应在醇溶剂中，反应速度快、转化率高，生成5－溴－6－甲氧基－2－丙酰基萘的收率高（98．59％）。     

手性钛锆化合物在不对称合成中的应用

本文综述了近年来手性钛锆化合物在不对称合成中的应用, 特别是手性柄型金属钛和锆化合物在不对称合成中的应用。对这类催化剂的特点和前景作了简要介绍。