基于自适应方法的Sn/O/H/N/C/Cl反应机理简化

计算包含详细反应机理的复杂反应流问题仍然是十分费时的,已有的反应流计算方法通常采用简化的化学反应机理．传统的机理简化方法大多基于反应条件的稳态假设,如主量组分分析法等．近年来,一种基于自适应化学理论的机理简化的新方法被提出．该方法根据设定的化学精度要求,可实现详细反应机理的最优简化．对Sn/O/H/N/C/Cl详细反应机理的简化结果表明Sn CO_2=SnO CO和Sn O_2=SnO O为机理中影响Sn氧化最重要的两个基元反应．     

Sn(5P~(23)P_(0,1,2))与N_2O、Ar、N_2、He和O_2的碰撞截面实验研究

在分子束—气装置上用原子吸收方法测量Sn(5p~2~3P_(0,1,2))分子束强度随背景气体的压力变化,得到锡原子三个电子态Sn(5p~2~3P(0,1,2))与N_2O、Ar、He、N_2和O_2等五种粒子的总碰撞截面,并估算出Sn原子与O_2和N_2O的反应碰撞截面。为了探讨SnO分子的化学激光体系,近年来报导了有关Sn原子与N_2O在气相状态下的反应。但是Sn+N_2O反应生成电子激发态SnO的机理尚不清楚。本文将要报导Sn的三个电子态5p~2~3P_0、5P~2~3P_1、5p~2~3P_2(以下简写成为~3P_(0,1,2))与N_2O等五种粒子碰撞截面的研究.这对于探讨反应机理和Sn原子与其它粒子的相互作用提供了实验的依据。由于Sn金属很难汽化,并且低压下发光很弱。以前研究Sn与N_2O、O_2或其它分子的反应都是在较高压力的实验条件下进行的。由于在较高压力下各种碰撞过程都可能同时产生,对研究反应机理是不利的。而本实验则是在低压条件下,并使用原子吸收方法来监测Sn原子浓度随碰撞气体浓度的变化,从而得出各种碰撞截面。这一新的方法对于研究金属原子与其它分子碰撞的过程,即使是不发光的反应碰撞也是适用的。这一方法的另一特点是可以分辩出原子的不同态,便于研究态—态反应动态学。     

Au2Ag和AuAg2团簇对CO催化氧化反应的理论研究

本文采用密度泛函理论,对Au₂Ag和AuAg₂团簇催化CO的氧化反应机理进行了系统的研究.对CO+O₂→CO₂+O和CO+O→CO₂两个氧化反应,文中分别讨论了ER反应机理和LH反应机理,结果发现在CO+O₂反应中倾向于LH反应机理,而在CO+O反应中则倾向于ER反应机理.此外,在完整的CO氧化反应中,Au₂Ag团簇两个催化氧化反应过程中的势垒都很低,说明其有望成为良好的CO氧化催化剂.     

碱土金属氧化物阳离子2MO+(M=Ca,Sr,Ba)参与N2O与CO反应理论研究

本文采用UB3LYP/6-311G(2d) +SDD//CCSD(T)/6-311+ G(2d) +SDD方法,计算研究了气相中碱土金属氧化物阳离子2MO+ (M=Ca,Sr,Ba)参与N2O (X1∑+)+CO(X1∑+)→N2(X1∑g+)+CO2 (X1∑g+)的反应机理.通过计算亲氧性得到在三种氧化物阳离子中只有2CaO+从N2O得到O原子并传递给CO的过程是热力学允许的.碱土金属氧化物阳离子2MO+参与主题反应的机理通过以下两种方式进行,其一为2 MO+从N2O获取O原子生成2MO+,进而向CO提供O原子得到2MO+和CO2,该过程为催化反应机理;其二为2MO+先与N2O复合生成中间体IM1,之后IM1继续与CO复合生成中间体IM2',经过一系列反应过程最终生成2MO+,N2和CO2.通过对两种反应过程的热力学性质和动力学因素分析得到,2 MO+ (M=Ca,Sr,Ba)参与反应N2O(X1∑+)+CO(X1∑+)→N2(X1∑g+)+CO2(X1∑g+)的机理为后一路径,所得结果与实验观测相符.     

碱土金属氧化物阳离子2MO+(M=Ca, Sr, Ba) 介入N2O与CO反应的理论研究

本文采用UB3LYP/6-311G(2d)+SDD//CCSD(T)/6-311+G(2d)+SDD方法, 计算研究了气相中碱土金属氧化物阳离子2MO+(M=Ca, Sr, Ba)参与N2O (X1∑+) + CO (X1∑+) → N2 (X1∑+g) + CO2 (X1∑+g) 的反应机理. 通过计算亲氧性得到在三种氧化物阳离子中只有2CaO+从N2O得到O原子并传递给CO的过程是热力学允许的. 碱土金属氧化物阳离子2MO+参与主题反应的机理通过以下两种方式进行, 其一为2MO+从N2O获取O原子生成2MO2+, 进而向CO提供O原子得到2MO+和CO2, 该过程为催化反应机理; 其二为2MO+先与N2O复合生成中间体IM1, 之后IM1继续与CO复合生成中间体IM2', 经过一系列反应过程最终生成2MO+, N2和CO2. 通过对两种反应过程的热力学性质和动力学因素分析得到, 2MO+(M=Ca, Sr, Ba)参与反应N2O (X1∑+) + CO (X1∑+) → N2 (X1∑+g) + CO2 (X1∑+g)的机理为后一路径, 所得结果与实验观测相符.     

PODE/甲醇双燃料化学动力学简化机理研究

聚甲氧基二甲醚(PODE)和甲醇属于煤基高含氧燃料,两者有效组合燃烧可实现内燃机节能减排.本文以PODE3和甲醇作为表征燃料,通过使用反应路径分析、直接关系图法、敏感性分析法对详细PODE3反应机理进行简化获得PODE简化子机理,然后与甲醇反应机理、NOx和PAHs子机理耦合获得PODE/甲醇双燃料化学动力学简化模型(...     

单碰撞Sn+N_2O→SnO+N_2化学发光反应研究

引言在红外化学激光实现之后,人们开始寻求可见光化学激光。可见光化学激光波长短,光子能量高,光束方向性好。为了这一目的,广泛地研究电子跃迁化学发光反应.要弄清反应机理及产物初生态的电子——振转分布情况,深入地研究单次碰撞条件下的基元反应是完全必要的.楼南泉等已对Ba+N_2O在单碰撞条件下的化学发光,作了新的动态学研究.我们利用自制的一台高温多用途的原子束装置,研究了Sn+N_2O→SnO~(?)+N_2SnO(?)→Sno+hv反应,观测了初生态的光谱特点及随N_2O压升高的部分弛豫的光谱概貌,我们从光谱图定量地获得了各电子态产物的振动布居。     

并行建表化学加速算法研究及其在气相斜爆轰模拟中的应用

采用详细化学反应机理对气相斜爆轰问题开展数值计算时,由于组分之间的特征时间尺度相差很大,反应源项的直接积分(direct integration,DI)求解通常存在强烈的刚性及非线性现象,导致计算量很大.为了在不损失计算精度的基础上有效减少化学反应过程的计算时间,针对包含2H2+O2详细机理的二维斜爆轰并行计算,提出两...     

O(1D)+N2O→NO+NO反应的理论研究

应用三体模型及扩展的LEPS势能面(PES),对初始条件为(Ecol=55 kJ/mol,v=0,j=0)的O(1D)+N2O→NO+NO反应体系进行了准经典轨线(QCT)计算.根据计算结果对体系的势能面及反应机理进行详细的分析和讨论,较全面地研究了此反应体系的动力学特征.     

SiCl_4/H_2/O_2反应动力学及其化学加速计算

本文提出了一个SiCl_4/H_2/O_2反应动力学模型,并采用H_2/N_2/SiCl_4-N_2/O_2层流对冲扩散火焰实验验证提出的详细机理的准确性,结果表明提出的详细机理获得的结果与测量结果较吻合。该详细机理被应用于熔石英玻璃合成仿真,与四步总包机理相比该详细机理获得了更低且更准确的温度及二氧化硅质量分数。为了在仿真中加快化学计算,本文研究了自适应建表与动态自适应化学的组合化学加速算法TDAC,得出采用TDAC算法能够获得加速因子为2.0的加速效果,且除了SiO_2含量预测有小的偏差外,温度和OH含量预测均较准确。TDAC引起的误差可以通过自适应建表的容差值及DAC的简化阈值进行有效控制。另外,TDAC中初始搜索组分选择对机理简化结果有重要影响,最终产物SiO_2是影响简化结果的关键组分之一,应该被包含在初始搜索组分中。     

Electro-oxidation of ethylene glycol on PtSn/C and PtSnNi/C electrocatalysts

A PtSn/C electrocatalyst with a Pt–Sn molar ratio of 50:50 and A PtSnNi/C electrocatalyst with a Pt–Sn–Ni molar ratio of 50:40:10 were prepared by alcohol-reduction process using ethylene glycol as solvent and reducing agent. The electrocatalysts were characterized by energy dispersive X-ray, X-ray diffraction, and cyclic voltammetry. The electro-oxidation of ethylene glycol was studied by cyclic voltammetry and chronoamperometry using the thin porous coating technique. PtSnNi/C electrocatalyst showed a superior performance compared to PtSn/C electrocatalysts in the potential range of interest for a direct ethylene glycol fuel cell.     

C/C复合材料的光谱发射率研究

采用模压成型法制备了不同类型的C/C复合材料,测试了其法向光谱发射率的变化.结果表明,短切碳纤维增强的C/C复合材料,其法向光谱发射率在整个2 500～13 000 nm的测试波段内普遍要高于碳布增强复合材料样品.短切碳纤维结构的相对松散,单位体积内物质的粒子数相对较少,这增加了电磁波的穿透深度,从而使得样品的法向光谱发射率较高,热辐射特性较好.纤维预制体和C/C复合材料样品的法向光谱发射率测试对比可知,两种不同碳材料的微结构差异使得树脂碳的法向光谱发射率优于纤维碳.利用Raman光谱对不同碳物质进行物相分析表明,树脂碳以sp3和sp2杂化态碳原子的混合结构使其内部产生的局域振动模式较多,这也是样品法向光谱发射率较高,热辐射特性较好的原因.     

Observation/confirmation of hindered E2 strength in 18C/16C

We have measured the lifetime of the first excited 2⁺ state in ¹⁸C using an upgraded recoil shadow method to determine the electric quadrupole transition. The measured mean lifetime is 18.9±0.9 (stat)±4.4 (syst) ps, corresponding to B(E2;2₁ ⁺ $ \rightarrow$ 0⁺ _gs) = 4.3±0.2±1.0e ² fm^4, or about 1.5 Weisskopf units. The mean lifetime of the first 2⁺ state in ¹⁶C was remeasured to be 18.3±1.4±4.8 ps, about four times shorter than the value reported previously. The discrepancy is explained by incorporating the $ \gamma$ -ray angular distribution obtained in this work into the previous measurement. The observed transition strengths in ^{16, 18}C are hindered compared to the empirical values, indicating that the anomalous E2 strength observed in ¹⁶C persists in ¹⁸C .     

C60,C60/C70混合物在甲苯和1－甲基萘中的荧光光谱

测量了C60,C60/C70混合物分别在甲苯和1-甲基萘中的激发谱和荧光光谱,用532nm波长光为激发源。比较了纯C60及C60/C70混合物的荧光特性,对所观察到的发光谱进行了讨论。     

Crystalline structure of a C60/C70 membrane

The crystalline structure of a C₆₀/C₇₀ membrane prepared by an original technique has been studied by x-ray diffraction and Raman spectroscopy. The effects of purification of the starting C₆₀/C₇₀ mixture to C₇₀ composition and of spatial separation of the C₆₀ and C₇₀ phases in the membrane have been revealed. The samples studied were established to have a composition gradient from C₆₀ to C₇₀. The main structure of the membrane is shown to be an fcc lattice with a=14.308 Å.     

Laser-induced chemistry in silane-hexafluoroacetone mixtures for production of novel Si/C/F/O and C/F/O materials

Chemical reactions induced by CO₂-laser radiation in mixtures of silane and hexafluoroacetone afford various gaseous silicon- and carbon-containing compounds and result in deposition of microstructures of carbon, C/F/O and Si/C/O/F materials. These products are suggested to be formed by a variety of exothermic reactions initiated through SiH₄-photosensitized decomposition of hexafluoroacetone. Silane is shown to be a very potent reagent for the reduction of C-F bonds.     

TCNQ/C_(60)及MB-PPV/C_(60)等组合薄膜的拉曼光谱

ＴＣＮＱ／Ｃ６０及ＭＢ┐ＰＰＶ／Ｃ６０等组合薄膜的拉曼光谱钱江单福凯钱士雄魏彦峰黄大鸣华中一（复旦大学物理系上海２００４３３）ＲａｍａｎＳｐｅｃｔｒａｏｆＴＣＮＱ／Ｃ６０ａｎｄＭＢ┐ＰＰＶ／Ｃ６０ＣｏｍｂｉｎａｔｉｏｎＦｉｌｍｓＱｉａｎＪｉａｎｇ，Ｓ...     

X-ray properties and interface study of B4C/Mo and B4C/Mo2C periodic multilayers

We present a comparative study of B₄C/Mo and B₄C/Mo₂C periodic multilayer structures deposited by magnetron sputtering. The characterization was performed by grazing incidence X-ray reflectometry at two different energies and high resolution transmission electron microscopy. The experimental results indicate the existence of an interdiffusion layer at the B₄C-on-Mo interface in the B₄C/Mo system. Thus, the B₄C/Mo multilayers were modeled by an asymmetric structure with three layers in each period. The thickness of B₄C-on-Mo interfacial layer was estimated about 1.1 nm. The B₄C/Mo₂C multilayers present less interdiffusion and are well modeled by a symmetric structure without interfacial layers. This study shows that B₄C/Mo₂C structure is an interesting alternative to B₄C/Mo multilayer for X-ray optic applications.     

The CC stretching band ν6 of allene-d4

The infrared spectrum of C₃D₄ was measured in the region of the paralled band of the CC stretching vibration ν₆ centered at ν₀ = 1920.2332 cm^?1 on a high-resolution Fourier transform spectrometer and deconvolved to a linewidth of $\text{～}\text{1}\text{2}$ of the Doppler width (～0.0023 cm^?1). The high resolution reveals the presence of strong perturbations in the K = 4 and K = 8 to 12 levels of the ν₆ upper state. For a quantitative treatment of the observed transitions, a Hamiltonian matrix including six different perturbing states was constructed and used to refine the 6 spectroscopic constants of the ν₆ state and 20 of the constants for the perturbing states. Measurement of the hot band ν₆ + ν₁₁ ? ν₁₁ whose band center is at 1916.200 cm^?1 yielded the anharmonic constant x_6,11 = ?4.033 cm^?1.     

Al/CdSe/GaSe/C resonant tunneling thin film transistors

An Al/CdSe/GaSe/C thin film transistor device was prepared by the physical vapor deposition technique at a vacuum pressure of 10⁻⁵ mbar. The x-ray diffraction measurements demonstrated the polycrystalline nature of the surface of the device. The dc current-voltage characteristics recorded for the Al/CdSe/C and Al/CdSe/GaSe/C channels displayed a resonant tunneling diode features during the forward and reverse voltage biasing, respectively. In addition, the switching current ratio of the Al/CdSe/C increased from 18.6 to 9.62×10³ as a result of the GaSe deposition on the CdSe surface. Moreover, the alternating electrical signal analyses in the frequency range of 1.0 MHz to 1.8 GHz, showed some remarkable properties of negative resistance and negative capacitance spectra of the Al/CdSe/GaSe/C thin film transistors. Two distinct resonance-antiresonance phenomena in the resistance spectra and one in the capacitance spectra were observed at 0.53, 1.04 and 1.40 GHz for the Al/CdSe/C channel, respectively. The respective resonating peak positions of the resistance spectra shift to 0.38 and 0.95 GHz when GaSe is interfaced with CdSe. These features of the thin film transistors are promising for use in high quality microwave filtering circuits and also for use as ultrafast switches.