Re（CO）3（L）系列配合物的成键和结构

借助于G03W程序包,对系列氨基羧酸分子的羰基铼配合物进行了结构优化,并对其中的相关能量、键长、键角、布局数等进行了研究.计算结果表明:各配合物相对于羰基铼中间体均具有一定的稳定性;配体分子结构中含有杂环或者较多数目杂原子时,有形成相对更稳定配合物的趋势;配体分子结构中应含有适宜的间隔体,否则需经较大的结构扭转或局部原子的拥挤方可形成相应配合物.     

TiO基态 (X 3 Δr) 的势能函数与光谱常数

应用群论及原子分子反应静力学方法推导了TiO分子基态(X³Δ_r)的离解极限.采用不同的计算方法,包括密度泛函B3LYP,B3P86,BP86,B3PW91和MP2,MP4方法,结合不同基组计算了TiO分子基态的平衡核间距、能量和振动频率.研究表明,使用B3LYP方法,对O原子使用6-311+G基组,Ti原子使用6-311+ +G^**基组时计算得到的平衡几何结构、分子离解能和谐振频率与实验值符合得最好.使用优选出的方法和基组对T 关键词： TiO 势能函数 光谱常数 密度泛函理论     

相转移催化无溶剂合成N-(ω-溴烷基)邻苯二甲酰亚胺

本文以N-(3-溴丙基)邻苯二甲酰亚胺合成为模板反应,研究了相转移催化无溶剂合成N-(ω-溴烷基)邻苯二甲酰亚胺的影响因素,实验证实相转移催化剂及其用量、催化剂K2CO3的用量等对反应的影响明显,得到N-(3-溴丙基)邻苯二甲酰亚胺的优化合成条件为:反应物配比为PA∶C3Br2∶K2CO3∶TBAB=1∶2∶4∶0.2,反应温度80℃,反应时间1h,N-(3-溴丙基)邻苯二甲酰亚胺产率为92%。在相同反应条件下,N-(ω-溴烷基)邻苯二甲酰亚胺的产率随α,ω-二溴烷烃的烷基链长度增加而降低。     

钛-钒合金及其氢化物的第一原理研究

用局域密度泛函近似 ( L DA)与赝势方法研究了钛钒合金氢化物的结构与组成的关系。结果表明 ,V的含量小于 30 % ,Ti- V合金将不能稳定在 bcc向 bct转化 ,含 Ti量高于 70 %的 Ti- V合金氢化物不能稳定在 bcc相。所计算的各种 Ti- V氢化物的体胀率小于 2 .5% ,比相同含 H量的纯 V氢化物的体胀率小 ,Ti- V合金有利于抗氢脆 ,但不利于对氢的贮存。     

Simulation of Helium Behaviour in Titanium Crystals Using Molecular Dynamics

The behaviour of helium in Ti crystals at 300 K has been investigated by means of the molecular dynamics. The study is focused on the influences of He-Ti interaction on the aggregation of helium atoms in the substrate. When a Born-Mayer potential is used to describe the He-Ti interaction, the He atoms are unable to cluster with each other due to the weak bridge barrier that cannot trap the helium atoms, Whereas using a He-Ti potential that is constructed by fitting the ab initio pairwise He-Ti potential, the clustering of He atoms can be observed. The results indicate that suitable He-Ti potential plays an important role in the formation of He clusters in metals. Moreover, it is noted that the shape of the formed He cluster is irregular, and the produced defect prefers to congregating on one side of the He cluster rather than spreading symmetrically around it.     

Hydrogenation Properties of Zr Films Under Various Conditions of Hydrogen Plasma

The hydrogenation properties of Zr samples with and without an Ni overlayer under various plasma conditions were investigated by means of non-Rutherford backscattering and elastic recoil detection analysis.The theoretical maximum hydrogen capacity,66.7 at%,could be achieved at a hydrogen absolute pressure of-2Pa and a substrate temperature of-393K for a plasma irradiation of only 10min;this was significantly greater than that for gas hydrogenation under the same hydrogen pressure and substrate temperature.It was also found that the C and O contamination on the sample surface strongly influences the hydrogenation,and that the maximum equilibrium hydrogen content drops dramatically with the increasing total contamination.In addition,the influence of the Ni overlayer on the plasma hydrogenation is discussed.     

镧系金属一氢化物有效芯势研究

采用Cundari和Stevens等推导的有效芯势对镧系金属一氢化物进行了理论计算，以探讨镧系金属元素与氢的相互作用。结果表明所有镧系金属一氢化物基态时理论上是稳定的，最稳定的是SmH,最不稳定的是DyH;键长计算结果显示，基态时镧系金属一招兵买马花物有独立王国 收缩现象发生；红外振动频率理论计算值与实验结果一致；成键轨道中，金属原子轨道的贡献主要是s轨道和d轨道：从CeH至ErH(GdH)例外）随着外层电子的增加s轨道成分逐渐增大d轨道成分逐渐减小；从TmH和LuH（包括GdH)，成键轨道中金属原子轨道的贡献主要是d轨道，约为90％；约大多数镧系金属一氧化物的成键轨道中金属原子轨道f成分小于1％。     

Effects of Substrate Temperature on Helium Content and Microstructure of Nanocrystalline Titanium Films

Helium-charged nanocrystalline titanium films have been deposited by HeAr magnetron co-sputtering. The effects of substrate temperature on the helium content and microstructure of the nanocrystalline titanium films have been studied. The results indicate that helium atoms with a high concentration are evenly incorporated in the deposited titanium films. When the substrate temperature increases from 60℃ to 350℃ while the other deposition＇parameters are fixed, the helium content decreases gradually from 38.6 at.% to 9.2at.%, which proves that nanocrystalline Ti films have a great helium storage capacity. The 20 angle of the Bragg peak of （002） crystal planes of the He-charged Ti film shifts to a lower angle and that of （100） crystal plane is unchanged as compared with that of the pure Ti film, which indicates that the lattice parameter c increases and a keeps at the primitive value. The grain refining and helium damage result in the diffraction peak broadening.     

涂膜超声及涂膜电解对固体表面铀的去污研究

制备了高分子可剥离去污膜液，确定了涂膜液中各组分最佳含量，对固体表面核素的去除研究结果表明：在金属表面采用涂膜电解去污、非金属光滑固体表面采用直接涂膜去污、非金属粗糙固体表面采用涂膜超声去污工艺，其去污率均可达99％以上，优于其他方法。     

He原子在金属Ti中行为的第一性原理计算

采用基于量子化学基本原理的密度泛函理论，研究He原子在金属T冲的占位、能量及结构优化后材料各性质参数的变化情况，以及He原子聚集成泡的微观原因。