C59(C6H4CH3)N的结构、UV-VIS光谱、NMR谱以及非线性光学性质的理论研究

用ＩＮＤＯ 系列方法对由（Ｃ５９Ｎ）２和甲苯合成的衍生物Ｃ５９ （Ｃ６Ｈ４ＣＨ３）Ｎ进行了理论研究,得到了分子的稳定构型,表明Ｃ５９（Ｃ６Ｈ４ＣＨ３）Ｎ具有Ｃｓ对称性。以优化构型为基础讨论了分子的ＵＶ－ＶＩＳ光谱、ＮＭＲ谱,结果与实验符合得很好。还计算了Ｃ５９－（Ｃ６Ｈ４ＣＨ３）Ｎ的二阶非线性光学系数βμ,结果表明这种分子具有较大的二阶非线性光学系数。     

Ar、NO和CHBr3对电子激发态CH的淬灭

The collisional quenching rate constants of CH(A, V'=0) by Ar and CHBr_3 and CH(A, B, V'=0) by NO molecule were measured by means of laser photolysis of CHBr_3 molecule at 266 nm generating CH(A, B) radicals and monitoring the time-resolved signal of ethession CH(A, B→X). The dependence of quenching rate constant of CH(A, V'=0) by CHBr_3 on rotational state of CH(A) is presented. It is found that the quenching rate decreases with increasing rotational quantum number of CH(A).     

CH2Cl与OH自由基反应机理的理论研究

The reaction mechanism of CH2Cl radical with OH radical to produce HCCl+H2O,HCOCl+H2 and H2CO+HCl has been studied by using quantum chemistry ab initio calculations. The optimized geometrical parameters,and vibrational frequencies of all species were obtained at the UMP2（FC）level of theory in conjunction with 6-311++G* basis set. Besides,the zero-point energies（ZPE）,relative energies and total energies of all species were calculated using Gaussian-3（G3）model. The results of theoretical study indicate that the activated intermediate CH2ClOH is first formed through a barrierless process,followed by atoms migration,radical groups rotation and bonds fission to produce HCCl+H2O,HCOCl+H2 and H2CO+HCl,respectively. And all channels are exothermic by 72.81,338.54 and 354.08 kJ/mol. The reaction heat of reactants to H2CO+HCl is 281.27 kJ/mol more than that of reactants to HCCl+H2O. This result accords with that of experiments.     

CH2FCF3与O(1D)反应机理的理论研究

用量子化学密度泛函理论(DFT)和G3(MP2)B3方法,对O(1↑D)与CH2FCF3的反应进行了研究．在UB3LYP/6-31G(d)计算水平上,优化了反应势能面上各驻点的几何结构,在G3(MP2)B3水平上进行了单点计算,并利用UB3LYP/6-311 G(3df,3pd)计算的波函数进行了电荷密度分析．通过内禀坐标(IRC)计算和振动分析,对反应过渡态进行了确认,并确定了反应机理．     

甲烷气体传感器的性能研究

本文研究了材料和工艺对甲烷气体传感器性能的影响。结果表明,当气体探测元件涂Pt-Pd复合催化剂而参比元件用Al2O3制作时,传感器的性能良好。     

Changing Rules of Bonding Electron Pair Correlation Energies of CH3X （X = F, OH, NH2） Systems

1 INTRODUCTION It has been known that the electron correlation energy of molecular systems was, and still is, one of the most serious bottleneck problems to the chemis- try accuracy of computational quantum chemistry. Since L鰓din[1] gave the definition …     

介质阻挡放电等离子体辅助CuO/CeO2-TiO2/r-Al2O3

在介质阻挡等离子体放电(DBD)辅助催化剂(6%CuO/15%TiO2/γ-Al2O3,6%CuO/5%CeO2/15%TiO2/γ-Al2O3)反应装置上,研究了4种不同反应条件下(NO+CH4,NO+CH4+O2,NO+CH4+NTP,NO+CH4+O2+NTP)NO和CH4反应,采用BET、XRD、H2-TPR和XPS等手段对催化剂进行了表征.结果表明在上述4种反应条件下,对于NO+CH4的反应,O2的存在有利于NO脱除,在等离子体条件下,O2的加入对NO的转化有所抑制;而等离子体的活化极大增强了NO的低温脱除活性.在等离子体存在条件下,6%CuO/5%CeO2/15%TiO2/γ-Al2O3(6Cu5Ce15TA)对NO的转化率都优于6%CuO/15%TiO2/γ-Al2O3(6Cu15TA).BET结果显示添加TiO2和CeO2于γ-Al2O3表面后,比表面积都有少量降低;而各载体负载6%CuO后比表面积也有所下降.XRD结果表明6Cu15TA和6Cu5Ce15TA催化剂由锐钛矿相TiO2组成,CuO在各催化剂表面呈现高度分散.H2-TPR数据和XPS实验结果显示负载CuO后,催化剂表面的铜物种由高度分散的CuO和嵌入到CeO2或TiO2晶格中Cu2+所组成.6Cu5Ce15TA表面含有较6Cu15TA多的Cu+,从而增强了NO的脱除活性.     

氢气比例和点火能量对CH4-H2混合气体爆炸强度影响的实验研究

在20 L标准球形爆炸罐内开展了当量比为1的甲烷-氢气-空气混合气体爆炸实验,通过改变点火能量和氢气体积分数,探讨点火能量和气体比例对其爆炸压力和爆炸强度的影响。研究发现:氢气比例越高,爆炸冲击波传播速度越快,点火能对冲击波传播速度的影响相对较小;点火能量的提高对峰值超压有增强作用,氢气比例低时,此增强作用较显著,氢气比例高时,此增强作用较弱;点火能量对爆炸强度指数KG的影响较小,而氢气比例对爆炸强度指数KG的影响十分明显,氢气比例低于50%时,氢气比例的增加对爆炸强度的增强作用较弱,氢气比例高于50%时,氢气的增加对爆炸强度的激励作用急剧增强。另外发现,相同当量比条件下,氢气的爆炸强度指数近似为甲烷爆炸强度指数的10倍。     

Synthesis of Polysubstituted Ferrocenesulfoxides

The purpose of the study is to design synthetic methodologies, especially directed deprotometalation using polar organometallic reagents, to access polysubstituted ferrocenesulfoxides. From enantiopure 2-substituted (SiMe₃, PPh₂) S-tert-butylferrocenesulfoxides, a third substituent was first introduced at the 5 position (SiMe₃, I, D, C(OH)Ph₂, Me, PPh₂, CH₂NMe₂, F) and removal of the trimethylsilyl group then afforded 2-substituted ferrocenesulfoxides unreachable otherwise. Attempts to apply the “halogen dance” reaction to the ferrocenesulfoxide series led to unexpected results although rationalized in light of calculated pK_a values. Further functionalizations were also possible. Thus, new enantiopure, planar chiral di- and trisubstituted ferrocenes have been obtained, in addition to several original 2-substituted, 2,3- and 2,5-disubstituted, 2,3,5-trisubstituted and even 2,3,4,5-tetrasubstituted ferrocenesulfoxides, also enantiopure.     

空气CH4浓度变化及其与CO的相关性

CH4是一种重要的温室气体,在空气中的含量仅次于CO2.化合物之间的相关性在化合物的浓度测量和估算等方面都有重要的意义.通过分辨率为1 cm-1的长开放光路傅里叶变换红外光谱仪测量采样路径内的北京西四环高速公路附近空气CH4和CO透过率光谱,进行非线性最小二乘光谱拟合,计算出待测组分浓度.北京秋季空气CH4浓度变化趋势几乎一样.白天的浓度变化趋势表明城市中人为活动对CH4的排放影响极大,尤其是机动车尾气的排放,而晚上浓度主要是近地面的积累.2005年9月4日到2005年9月10日的连续浓度变化表明北京秋季每天CH4和CO浓度变化趋势相同,它们的浓度变化具有一定的相关性.