高灵敏度无机分光光度法

前言对于分析方法,特别是工业分析方法,一般都希望不使用价格昂贵的特殊装置;操作简便;不论何人、何时、何地使用均能得到可靠的数据。而分光光度法在相当程度上能满足这样的要求。虽然现在各种仪器分析方法得到了迅速的发展,但分光光度法仍然广泛应用于各个领域,日本工业标准等法定的分析方法亦采用分光光度法,其原因恐怕就在于此。如果能将分光光度法韵应用范围从以往的痕量成分分析扩大到超痕量成分分析,那将是非常理想的。从这个观点出发,     

Pt碘乙二胺配合物的DFT和DV-Xα研究

利用密度泛函DFT/LANL2DZ和DV-Xα，对两种Pt(IV)碘配合物trans，cis-[Pt (OAc)_2I_2(en)] (A)，trans，cis-[Pt(OH)_2I_2(en)] (B)及它们的光照产物 [Pt(OAc)_2(OH)I(en)] (C)，[Pt(OH)_3I(en)] (D)完成了几何优化；计算了配合 物能级、光谱、前线轨道组成、电荷布居等性质。计算结果能解释有关的实验现象 。     

聚合物{[CuII(Hpb) (mal)]H2O}n :单体的量子化学计算和磁性研究

{[Cu^Ⅱ（Hpb）（mal）]H=O}n （Hpb=2-2＇-pyridylbenzimidazole, mal=maleic acid） is a helical chain-like polymer complex. In order to investigate the electronic structure of the complex, the monomer Cu^Ⅱ（Hpb）（mal） was obturated with different functional groups respectively. For these selective segments, the geometry optimizations were conducted by using hybrid DFT （B3LYP）methods to find that the structure obturated with H2O was better consistent with the experiment, and then this model would be used to latter calculations, such as the frontier molecular orbital and the NBO charge population analysis. In addition the magnetic behaviors of this complex were analyzed by experiments and the weak antiferromagnetic couple between copper（Ⅱ） ions was observed. The exchange coupling constant was calculated by DFT based on the spin broken symmetry formalism. The calculated coupling constants were in good agreement with the experimental data.     

含芯电子相关能修正的G2理论——G2(ful)

A general method in considering the core electronic correlation energies has been proposed and introduced into the standard Gaussian-2 (G2)[7] theory by small post-Hartree-Fock calculations. In this paper an additional MP2(FC)/6-31G(d) calculation over the G2 procedures is employed and examined in modification in modification to the flaw of Frozen-Core (FC) approximation of G2 vai eq.:
ΔE(full)= E[MP2(full)/6-31G(d)]-E[MP2(FC)/6-31G(d)]
where the MP2(full)/6-31G(d) energy has been obtained in the molecular geometry optimizations. This energy, ΔE(full), is directly added into the total G2 energy of a molecule in facilitating the effect of core electronic correlations for each molecule in chemical reactions. It has been shown that the over-all average absolute deviation for the 125 reaction energies of the G2 test set (test set 1) is slightly reduced from 5.09 to 5.01 kJ, mol(-1) while for the 55 D0 values, which have been used for the derivation of the A coefficient of the empirical High-Level...更多-Correction (HLC), it is also reduced from 4.99 [for both G2 and G2(COMPLETE)[8]]to 4.77 kJ• mol(-1). In addition, larger errors (greater than ±8.4 kJ•mol(-1) for the D0 energies are improved, especially for the largest error of the D0 of SO2 This error is reduced from 21.3 to 15.4 kJ. mol(-1), in which the experimental geometry would further reduce it by 7.1kJ.mol(-1)[8]. Another improvement is the absolute value of the A coefficient in HLC being reduced from 4.81 for G2 to 4.34 milli-hartrees which is believed to be useful in isolating the relationship between the HLC and the FC approximation. Modifications to the original G2 from this work is denoted as G2(fu 1) and thus the G2 (fu 1) total energy for a molecule is
E[G2(fu 1)]= E[G2]+Δ E(full)h
with a new ΔE[HLC] =-0.19α- 4.34nβ milli-hartree.     

铂硅铝催化剂的铂分散度与催化性能的关系

研究了不同类型铂硅铝催化剂的铂分散度,并考察了它和催化剂的酸性及活性等相互之间的关系。发现当改变酸性或铂分散度时,催化剂的铂总面积和酸性以及活性三者之间都有平行变化的趋势。这些结果都可用表面复合体生成的观点解释,但与分离中心的观点有所矛盾。     

新型CuI-亚磷酸胺酯催化剂催化芳卤胺化反应的研究

芳胺类化合物是一类重要的有机化合物,它们广泛应用于生物学、药物学及材料学等领域[1-4].Buchwald[5,6]及Ma[7]等分别报道了N,N及N,O配体用于CuI催化的芳卤胺化反应,得到了较好的结果.对于亚磷酸胺酯N,P配体用于CuI催化的芳卤胺化反应至今未见文献报道.本工作采用新的合成方法,通过两步反应,很方便地合成了一系列的新型亚磷酸胺酯N,P配体,并用于CuI催化的芳卤胺化反应.     

C_(70)R_2(R=OH,CH_3)的结构和电子光谱

INDO方法研究了C70R2（R＝OH，CH3）4种异构体的结构和稳定性，表明1，9－C70（OH）2比7，8－C70（OH）2稳定，两者能量差为38．5kJ／mol，而7，8－C70（CH3）2比1，9－C70（CH3）2能量低23．0kJ／mol．以优化构型为基础，对C70R2（R＝OH，CH3）的电子光谱进行了理论预测．     

主动力信息足以确定静摩擦力的指向吗?

摩擦力既是教学的重点,更是教学的难点,特别是静摩擦力的指向确定。文章将阐述:首先,就计算而言,静摩擦力指向确定并不重要;第二,对某些动力学问题,主动力信息不足以唯一确定静摩擦力的指向;第三,在某些特殊条件下,比如运动刚体的质心位于接触点法线上(如无质量偏心的圆柱),由主动力向撞击中心简化的主矩可确定静摩擦力的指向;第四,把摩擦面假想成光滑面后,运动刚体在接触点的切向加速度指向与该处静摩擦力的指向相反。     

反导火力单元空间杀伤区内拦截概率研究

拦截概率是评价反导作战效能的重要指标,对交战前任务规划至关重要。选取某一拦截弹建立其在空间的可达集区域,针对中段反导逆轨拦截情况,确立其在空间中的杀伤区。针对杀伤区内任一点可能为拦截点的情况,对某一来袭导弹的弹道轨迹,选取可拦截弧段上的理论拦截点,通过在选取不同高度上的理论拦截点上,调整拦截弹的发射位置,从而得到拦截点在杀伤区内不同高度,不同距离以及在不同的交汇角时对拦截概率的影响。为反导作战的阵地部署研究和交战策略提供了一定的参考。     

低β 162.5 MHz taper型HWR腔的机械性能分析（英文）

北京大学正在设计β=0.09,频率为162.5 MHz taper型的二分之一波长射频超导谐振腔(HWR腔),这种腔针对高流强质子束(约100mA)和氘束(约50mA)的加速而设计。对于这种超导腔而言机械性能分析是十分重要的,可以通过机械性能分析来估计由于腔体的形变带来的频率偏移。用ANSYS分析了由于液氦压力不稳定造成的麦克风效应以及洛伦兹力造成的腔体失谐,并且对沿腔体轴线方向的调谐进行了分析。模拟结果显示这只腔压力敏感系数为31.1 Hz/kPa,洛伦兹力系数为-0.41Hz/(MV·m~(-1))~2。腔体的调谐范围达到±177kHz,足够补偿腔体可能的频率偏移。腔体的机械性能满足腔体正常运行的要求。