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。     

应用不同光谱技术,动物RBC,Hb及人皮肤表面血流氧化-还原状态检测

目的:检测与分析实验动物血液RBC(RBC·O2,RBC·CO2),Hb(HbO2,HbCO2)和人体皮肤表面流动血液氧化·还原状态的成像与未成像可见光谱领域OD值特征,并为该技术对白癜风病表皮黑色素颗粒检测中的应用尊定基础。方法:利用不同光谱技术和invitro和invivo检测手段,统计分析血液不同状态下波长与位置的OD值信息。结果:invitro检测:动物血液Hb·O2和RBC·O2两者在可见领域均有367,414(Soret带)nm与541,576(Q带)nm的吸收峰位;血液Hb·CO2和RBC·CO2均有432(Soret带)与和553(Q带)nm的波长吸收峰位;血液RBC状态和Hb溶血状态波长吸收峰位无改变,只是在氧化与还原状态下有完全独立的吸收峰位,血液RBC状态和Hb溶血状态波长吸光度OD值之间,有显著性差异(p<0·01)。浓度为1·5×107cell·mL-1的RBC·O2和Hb·O2在576nm的吸收峰位吸光度(y)与红细胞浓度(x)做成两条回归曲线:既,Hb·O2(b1)^y=0·05 0·983x;RBC·O2(b2)y^=0·127 1·934x,两者之间差异有显著性(p<0·01)。invivo检测:在人手背皮肤表面ImSpector图像中RBC·O2状态在540,576nm,RBC·CO2状态在555和755nm处有吸收峰。选择(a:指甲,b:指,c:手背)三个点位分别进行波长检测,每点(n=10)545nm吸收峰的平均OD值,依次为0·83±0·001,0·73±0·001和0·62±0·001,其三处测定点的OD值之间有显著性差异(p<0·01)。结论:invitro检测的RBC与Hb两者波长吸收峰位不变,但吸光度OD值不同,认为RBC状态测定结果更接近于活体组织血管内原始状态。invivo检测对人体无任何侵袭与损伤,灵敏度高,测试时间短,并且同时获得被测样品的波长与位置信息画面等优势,有望表皮中黑素等有色颗粒的直接检测。     

Impact on the magnetic compressor due to CSR

When an electron bunch is compressed in a chicane compressor, the CSR (coherent synchrotron radiation) will induce energy redistribution along the bunch. Such energy redistribution will affect the longitudinal emittance as a direct consequence. It will also excite betatron oscillation due to the chromatic transfer functions, and hence a transverse emittance change. So, it is indispensable for us to find a way to alleviate the CSR-caused emittance dilution and the bad result of chicane compressor in PKU-FEL.     

高斯光束非线性“热像”效应研究

高功率激光系统中非线性“热像”强度可能达到光学元件损伤阀值，从而对系统的安全运行造成威胁.以往的非线性“热像”现象研究都是基于无限大平面光波背景，但实际系统中传输的是有限束宽光束.本文以高斯光束为例，基于无像差自聚焦理论分析了有限束宽光束的“热像”形成规律.结果表明，高斯光束“热像”的强度与位置在光束腰斑较小时与平面光波情况有明显不同，但光束腰斑较衍射物大得多时，高斯光束可以近似当作平面光波处理.     

聚酰胺酸合成工艺研究

 采用超声波在线测量溶液粘度的方法，研究了合成聚酰胺酸过程中实验条件的影响，并对实验结果进行分析，由此确定了合成高分子量聚酰胺酸的最佳实验条件。研究表明：在加料次序为先加二胺后加二酐（二酐与二胺的摩尔比为1.01～1.02：1）、试剂中含水量尽可能少，反应温度0～5℃、反应时间以溶液粘度到达最大值为止的条件下，所合成的聚酰胺酸溶液粘度最大，可满足惯性约束聚变（ICF）充气腔靶端口膜的需要。     

Mn（Ⅱ）,Co（Ⅱ）与HSA相互作用的荧光光谱研究

用荧光光谱法研究了生理ｐＨ和等离子点（ｐＨ＝５．３０）时Ｍｎ（Ⅱ）、Ｃｏ（Ⅱ）与ＨＳＡ的相互作用。根据Ｆｏｒｓｔｅ非辐射能量转移理论,得到了不同ｐＨ时Ｍｎ（Ⅱ）、Ｃｏ（Ⅱ）在ＨＳＡ中的第一强结合位置与Ｔｒｐ－２１４残基间的距离。这一结果远大于文献报道值,根据Ｍｎ（Ⅱ）、Ｃｏ（Ⅱ）在ＨＳＡ中的结合部位及ＨＳＡ的畴结构对这一显著差异进行了讨论。     

微腔内气体抽离的多尺度模拟与分析

基于适用于整个克努森数范围的流动理论,建立了去除惯性约束聚变实验中靶丸内空气的理论模型,并设计实验验证了此模型的可靠性。物理实验要求靶丸内空气浓度低于10×10⁻⁶,数值模拟了去除靶丸内空气的过程,重点分析了靶丸内空气浓度、压力与除气时间的关系。计算并比较了单管路一次抽气法、单管路循环抽气法与双管路流洗法三种去除靶丸内空气方法的时间成本。数值计算结果表明：单管路一次抽气法中,靶丸上的微通道的存在对去除靶丸内空气所需时间的影响不可忽略,在考虑靶丸上微通道与充气管的情况下,需要1961.77 h才能使靶丸内的空气浓度达到标准。单管路循环抽气法中,抽气次数与单次抽气程度会影响去除靶丸内空气所需总时间,在单次抽气程度值取最优的情况下,采用充三次,抽四次的方案可使达标总时间减少至1 h左右,此方案下单次充气和抽气时间分别为6 min和10 min。而采用双管路流洗法则仅需11 min便可使靶丸内空气浓度达标。     

GFC-空间中的GFs-KKM定理及其对重合问题的应用（英文）

在GFC-空间中引入GFs-KKM映射,建立GFs-KKM定理.作为应用,获得GFC-空间中广义γ-GFs-对角拟凹弱γ-转移紧下半连续泛函的变分不等式、弱转移紧闭集的几何截口定理和弱转移紧开值集值映射的重合定理.我们的结论统一、改进和推广了一些近期文献的已知结果.