微波解离氯分子及其解离率的研究

 通过微波解离Cl₂与Ar的混合气来获得Cl原子，并对Cl₂解离率进行了测量。反应池内压力在200～253Pa范围变化时，可得到较多的Cl原子。当压力为256Pa时，Cl₂ 的解离率可达8%以上。但随着反应池内压力的增加，Cl₂解离率反而下降，这可能是Cl原子发生复合的几率增大所致。     

微波放电解离氯分子解离效率的测量

 以Cl/Cl₂/HN₃/He为基础的NCl(a¹Δ)/I作为一种化学激光新的体系，氯原子产生的多少对该体系的研究是至关重要的。利用滴定法研究了微波解离氯分子的解离效率。用HN₃/He滴定Cl，由光学多通道分析仪监测NCl(a¹Δ)和NCl(b¹Σ)辐射的荧光。发现微波解离氯分子的效率并不是想象的那样低，在较小的氯流量下，最高的解离效率可以达到100％。     

丙烯醛在外电场中的解离性质

利用密度泛函理论（DFT）计算方法,在6-31G+（d,p）基组上,讨论C₃H₄O气体分子在受到外加电场（-10.28 V·nm^-1~10.28 V·nm^-1）作用时的结构特征和解离特性。计算发现,沿分子共轭单键的方向电场增强时,总能量增大,碳碳双键和碳碳单键的键长减小,碳氧双键键长增大,偶极矩减小;能隙E_G增加,红外吸收峰在不同的频率分别发生红移和蓝移,同时IR强度发生变化。分子解离性能表现为：势能壁垒随着外电场增大而降低,达到25.71 V·nm^-1时势能壁垒几乎消失,解离能随着电场增加而逐渐降低,说明在电场作用下解离难度逐渐减小。研究结果为C₃H₄O气体分子或含有该成分的混合物在外电场下的解离特性研究提供参考。     

二氧化碳分子的电子贴附解离

本文综述了我们在二氧化碳分子电子贴附解离动力学实验研究方面的进展. 首先,介绍电子贴附解离基本概念并列举二氧化碳研究已有的结果. 其次,研制相关仪器,特别是近两年来发展的高分辨装置. 再次,利用上述装置,我们系统开展了二氧化碳电子贴附解离动力学实验研究,并与他人的研究进行了分析比较. 最后,对火星原地制氧和二氧化碳催化转化等方面的潜在应用进行讨论并展望.     

S3解离中的非绝热过程

采用量子力学从头计算方法研究了硫的三聚物S3低激发态解离过程.构造了S3分子的解离极限.对态态间跃迁极矩的计算表明,在势能曲面的交叉区域态态间存在相互转换的非绝热过程,从而确定了在S3解离为S2的复杂过程中,非绝热预解离是重要的解离通道.     

异戊二烯解离光电离理论研究

利用CBS-QB3理论计算方法研究了异戊二烯的可能解离通道.获得了主要碎片离子C₅H₇⁺,C₅H₅⁺,C₄H₅⁺,C₃H₆⁺,C₃H₅⁺,C₃H₄⁺,C₃H₃⁺的C₂H₃⁺的结构以及这些解离通道的解离能,并给出了相应的过渡态和中间体的结构和位垒.得到的异戊二烯电离势及主要碎片离子的出现势均与实验值符合的较好.最后,通过理论和实验结果的对比讨论了各通道的解离机理.     

甲苯光电离解离理论研究

The photoionization and dissociation photoionization of toluene have been studied using quantum chemistry methods.The geometries and frequencies of the reactants,transition states and products have been performed at B3LYP/6-311++G (d,p) level,and single-point energy calculations for all the stationary points were carried out at DFT calculations of the optimized structures with the G3B3 level.The ionization energies of toluene and the appearance energies for major fragment ions,C₇H₇⁺,C₆H₅⁺,C₅H₆⁺,C₅H₅⁺,are determined to be 8.90,11.15 or 11.03,12.72,13.69,16.28 eV,respectively,which are all in good agreement with published experimental data.With the help of available published experimental data and theoretical results,four dissociative photoionization channels have been proposed:C₇H₇⁺+H,C₆H₅⁺+CH₃,C₅H₆⁺+C₂H₂,C₅H₅⁺+C₂H₂+H.Transition structures and intermediates for those isomerization processes are determined in this work.Especially,the structures of C₅H₆⁺ and C₅H₅⁺ produced by dissociative photoionization of toluene have been defined as chain structure in this work with theoretical calculations.     

丙酮激发态α解离的理论研究

利用密度泛函理论对丙酮分子基态和最低三重激发态的结构进行了构型优化和振动频率计算,并对丙酮三重激发态α解离反应进行了理论分析。     

羟基自由基双光子激发解离动力学

本文利用高里德堡态氢原子飞行时间探测技术,研究了羟基自由基的双光子激发解离动力学. H(²S)+O(¹D)和H(²S)+O(¹S)解离通道是由于羟基在经由A²Σ⁺(v''=2, J''=0.5-2.5)中间态通过双光子激发最终到排斥性的激发态势能曲线2²Ⅱ和B²Σ⁺上产生. 这两种解离通道产物都具有各向异性的角向分布,其中H(²S)+O(¹D)产物角分布异向因子β为-0.97,H(²S)+O(¹S)产物角分布异向因子β为1.97. 各向异性的角向分布与OH自由基在排斥性的激发态势能曲线上直接解离机理相吻合. 此实验观测到羟基自由基的解离能为35580±15 cm^-1.     

水在金属氧化物表面的吸附与解离

水(H2O)由H原子和O原子组成.地球上有大量的水,若能找到一种经济、实用的方法将H2O解离生成H2和O2,则在新能源的开发和应用方面,意义深远.水在固体表面的吸附现象极为普遍,在某些金属或金属氧化物表面,H2O被吸附并解离成OH-和H+.文章以有序氧化镁(MgO(100))薄膜和Pd/MgO(100)体系为例,在超高真空条件下,用光电子能谱和高分辨电子能量损失谱方法,研究了水在它们表面的吸附与解离.研究结果表明,H2O在MgO(100)表面可以被部分解离,而H2O在Pd/MgO(100)表面的解离与Pd的含量有关.了解水与固体表面的相互作用机理还需要做更多的基础研究工作.     

High-pressure-activated carbon tetrachloride decomposition

The pressure-induced molecular dissociation as one of the fundamental problems in physical sciences has aroused many theoretical and experimental studies. Here, using a newly developed particle swarm optimization algorithm, we investigate the high-pressure-induced molecular dissociation. The results show that the carbon tetrachloride （CC14） is unstable and dissociates into C2C16 and C12 under approximately 120 GPa and more. The dissociation is confirmed by the lattice dynamic calculations and electronic structure of the Pa3 structure with pressure evolution. The dissociation pressure is far larger than that in the case of high temperature, indicating that the temperature effectively reduces the activation barrier of the dissociation reaction of CC14. This research improves the understanding of the dissociation reactions of CC14 and other halogen compounds under high pressures.     

Resonance enhanced multiphoton ionisation (REMPI) detection of Cl(2Pj) atom in the photodissociation of halogenated pyrimidines at 235 nm: role of triplet states

ABSTRACT

The dynamics of chlorine atom (²P_j) formation in the photodissociation process of halogen substituted pyrimidines, namely, 2,4,6-trichloropyrimidine and 5-chloro-2,4,6-trifluoropyrimidine have been studied around 235?nm using Resonance Enhanced Multiphoton Ionisation Time-of-Flight Mass Spectrometry technique. For the chlorine atom dissociation channel, we have determined the translational energy distribution, the recoil anisotropy parameter, β, and the spin–orbit branching ratio. In both the molecules, the TOF profiles for Cl (²P_3/2) and Cl* (²P_1/2) are found to be independent of laser polarisation suggesting a zero value for β, within the experimental uncertainties. For 2,4,6-trichloropyrimidine, the average translational energies for Cl and Cl* elimination channels are determined to be 6.0?±?1.2 and 7.0?±?1.5 kcal/mol, respectively. Similarly, for 5-chloro-2,4,6-trifluoropyrimidine, the average translational energies for Cl and Cl* elimination channels are determined to be 6.5?±?1.2 and 7.9?±?1.6 kcal/mol, respectively. Computational calculations are performed to generate the potential energy curves along the dissociating C-Cl bond using equation of motion coupled cluster with single and double excitations (EOM-CCSD) method. Computational studies suggest the role of triplet states in the photodissociation process forming the Cl atom.     

磁控溅射Cl掺杂CdTe薄膜的孪晶结构与电学性质

CdTe用作薄膜太阳能电池吸收层需要经过氯处理才能得到高的光电转换效率,其中Cl原子的作用机理仍然没有完全被理解.实验发现Cl原子主要偏聚在CdTe晶界处,对晶界有钝化作用,而有第一性原理计算认为Cl原子掺入CdTe晶格能够引入浅能级提高光电转换效率.为了验证Cl原子掺杂是否对CdTe的光电转换效率有益,本文通过磁控溅射制备了100 ppm(ppm=1/1000000)Cl原子掺杂的CdTe(CdTe:Cl)薄膜并研究了薄膜的晶体结构与电学性质,同时对比了正常氯处理的无掺杂CdTe薄膜与CdTe:Cl薄膜之间的性质区别.实验发现Cl原子掺杂会在CdTe:Cl中形成大量仅由几个原子层构成的孪晶,电子和空穴在CdTe:Cl薄膜中没有分离的传导通道,而在氯处理后的CdTe薄膜中电子沿晶界传导,空穴沿晶粒内部传导.磁控溅射沉积的CdTe:Cl多晶薄膜属于高阻材料,退火前载流子迁移率很低,退火后载流子浓度降低到本征数量级,电阻率提高.CdTe:Cl薄膜电池效率远低于正常氯处理的无掺杂CdTe薄膜电池效率.磁控溅射制备的非平衡重掺杂CdTe:Cl多晶薄膜不适合用作薄膜太阳能电池的吸收层.     

Infrared multiphoton dissociation of 1,2-dichloroethyltrifluorosilane

Infrared multiphoton absorption and dissociation of 1,2-dichloroethyltrifluorosilane molecules under the action of pulsed TEA CO₂ laser were experimentally studied. The composition of dissociation products was analyzed. The only products of dissociation have been found to be stable molecules: chloroethylene and trifluorochlorosilane. Dissociation proceeds via chlorine atom transfer from carbon to silicon. The silicon isotope-selective infrared multiphoton dissociation was performed at different wavelengths of the CO₂-laser radiation. High degrees of silicon isotope separation have been achieved.     

低气压下XeCl准分子的形成研究

本工作利用高频介质阻挡放电对较低气压(70～1330 Pa)Xe/Cl_2混合气体中XeCl准分子的形成过程进行研究。通过探测不同Xe/Cl_2混合气压和不同Xe/Cl_2混合比条件下放电等离子体在285～315nm波长范围的荧光发射谱,得到了XeCl准分子在308nm附近的荧光发射以及荧光强度随气压变化曲线。得出该实验条件下生成XeCl准分子的最佳Xe/Cl_2混合比为4:1。     

The Kinetic Mechanisms of the Trapping of Atmospheric Gases by Marine Salt Surfaces: IX. The Heat of Adsorption of Cl Atoms on the Surface of NaCl

The heterogeneous trapping of chlorine atoms on the surface of NaCl was studied using two coaxial stream reactors connected to an EPR cavity or a mass spectrometer. The kinetics of trapping was measured by the EPR method over a wide range of chlorine atom concentrations (10¹⁰–10¹³ cm^?3) at temperatures of 250–330 K. At [Cl] ≥ 10¹² cm^?3, chlorine atoms were recorded by the EPR method in the gas phase. At lower concentrations (~10¹⁰?3 × 10¹¹ cm^?3), Cl atoms were replaced with RO₂ radicals by adding hexane RH and O₂ at the entrance of the EPR cavity. This was followed by the matrix isolation of RO² in the cavity at liquid nitrogen temperature. The probability of the trapping of chlorine atoms on the chemically inactive surface of NaCl was found to increase as the concentration of Cl grew. The temperature dependence of the trapping coefficient γ was pronounced at a concentration of chlorine atoms of ~3 × 10¹⁰ cm^?3, whereas no such dependence was observed at a chlorine concentration of ~ 10¹³ cm^?3. The recombination of Cl atoms was well described by the Rideal-Eley mechanism, and the heat of adsorption of chlorine atoms on the inactive surface of NaCl was estimated at Q = 17 ± 0.6 kcal/mol. It was shown mass spectrometrically that the trapping coefficient γ of Cl atoms decreased with the time of measurements, like the partial coefficient of the formation of the HCl product, whereas the partial coefficient of the formation of the Cl₂ product, conversely, increased with the time. The characteristic time of the attainment of stationary values by all the γ coefficients weakly depended on the initial concentration of Cl and equaled several dozen seconds. Reactions of adsorbed Cl atoms formed in the trapping of NO₃ radicals by the surface of marine salt NaCl in coastal troposphere are discussed.     

Influence of external electric field on the transfer of protons in hydrogen-bonded systems

The LCAO MO self-consistent field method in combination with the 6-31** basis set is used to calculate sections of the potential energy surface for a proton in the NH₃…HCl system in the presence of an external electrostatic field. The field strength is varied in the range of 0.000 to 0.017 a. u. In the absence of the field, the potential of the proton in the isolated complex has one well, the N–Cl distance is equal to 2.92 Å, and the NH₃…H–Cl bond is a hydrogen bond. With increasing distance between the N and Cl atoms, a second well appears in the potential, with the well near the Cl atom remaining deeper. In the presence of an external electric field, with increasing its strength, the depth of the well near the N atom increases, while the height of the barrier for proton transfer from the chlorine to the nitrogen atom decreases. At a certain field strength, the well near the nitrogen atom becomes deeper than that near the chlorine atom, so the proton moves to the nitrogen, making the complex ionic. Thus, the external electric field can influence the type of chemical bond in NH₃…HCl system.     

A Model for the Bulk Plasma in an RF Chlorne Discharge

A model has been constructed to describe the electrical characteristics of the central bulk plasma region in a 13.56-MHz parallel-plate discharge in chlorine at pressures of about 1 torr. This region is modeled as a volume-controlled plasma with the electron balance dominated by single-step electron-impact ionization and attachment and with the electron energy distribution function in equilibrium with the local instantaneous electric field. Relationships between the ionization frequency, the attachment frequency, the electron drift velocity, and the electric field are provided by solutions of the Boltzmann equation for mixtures of Cl2 and Cl which result from Cl2 dissociation. From a measured current waveform and Cl2/Cl density ratio, the model generates the local electric-field waveform, the time-varying electron density, and the power density in the central portion of the bulk plasma. The calculated time-averaged power input per unit discharge length compares well with experimentally determined values.