C2D2和C2H2分子键-键耦合研究

采用Morse根于描述C_2D_2分子中C－D键的伸缩振动，用谐振子描述C－C键伸缩振动，更新构造了C2D2分子的振动哈密顿，自行设计了非线性最小二乘拟合程序，并用它对C2D2分子的伸缩振动能级进行拟合，得到了基本的势能参数．理论计算与实验结果符合得很好，拟会的标准差为1.14cm－1；利用这些参数进一步计算了C2H2和C2D2的振动能级．     

H2X(X=O,S)分子简正模激发态下分子内能量转移的研究

采用准经典轨迹法,考察了H₂O及H₂S分子简正模激发态下分子内各态能量随时间变化的分布关系,讨论了激发能在各态间的转移规律.研究表明:简正模激发态能量转移倾向于频率彼此相近或对称性相同的态间.     

UF6分子的模型伸缩振动能级的计算

利用一个四参数非线性模型,对处于电子基态下的XY6型分子的X-Y键的伸缩振动进行了描述,并将其应用于计算UF6分子中U-F键的伸缩振动能级.计算中引入的模型Hamilton算符所包含的描述U-F键非谐振动的参数λ和描述U-F键之间的偶极-偶极相互作用参数ε1, ε2由实验值得出,波函数|ψn〉按形式为|n,α〉=|n1〉|n2〉|n3〉|n4〉|n5〉|n6〉的基函数集展开,从而把复杂的Hamilton方程转化为简单的矩阵代数方程.结果显示,该非线性模型能够较好地描述UF6分子的振动( 计算误差在1.0 cm-1之内 ),同时合理地预测了一些至今还未观测到的能级值.     

Ar2H+ 分子振动光谱的理论计算

基于近期由本组提供的Ar2H+分子的基态势能面,应用含时波包演化方法,计算了总角动量J=0时的振动光谱,并对其中的一些谱峰进行了指认.与现有的ab initio结果进行比较,这个新势能面包含了关于Ar2H+基态的比较正确的信息.     

H2O分子OH键振动能谱的代数计算

用U(2)代数模型,对H2O分子OH键的高激发振动能谱进行了理论计算,并与其它模型的计算相比较,结果表明,代数模型能以较小的标准偏差描述这一分子OH键的振动能谱.     

异丙醇的O-H伸缩振动泛频光谱和分子构像

使用高灵敏的光腔衰荡光谱(CavityRingDownSpectroscopy)技术测出了异丙醇的O-H伸缩v=4、5振动泛频光谱,每个振动能级都有三个吸收峰,被归属为分子构像的O-H伸缩泛频吸收.给出了光腔衰荡光谱的振动泛频吸收的谱带强度公式,并求得分子不同构像在不同振动能级的O-H伸缩泛频吸收的谱带强度;同时利用局域模理论,求得分子各O-H伸缩局域模振子的机械频率(X1)、非谐性(X2)以及解离能(D).用密度泛函(DFT)B3LYP/6-31+G*理论方法优化了分子的各种可能构像,验证了分子存在反式(trans)和偏转(gauche)两种稳定构像,计算的分子的O-H伸缩频率及构像稳定性同实验结果是一致的.     

CF_2自由基_态伸缩振动频率的测定

CF2自由基作为许多碳氟化合反应的中间物及它在大气化学中的影响而一直引起人们的研究兴趣同．自从1950年Venkateswarlu首次观测到它的光谱以来同，对CF2电子基态的理论及实验研究方面都有相当多的数据积累．特别是近年来高分辨红外光谱对CF2电子基态提供了结论性的数据[3,4]．     

CF2自由基A态伸缩振动频率的测定

Laser induced fluorescence excitation spectroscopy has been used to determine the previously ambiguous assignments of A-state stretching frequencies of CF2 radical under supersonic free jet conditions. The measured frequencies are v’1=1012.1±0.5cm-1, v’3=1180.2±0.5cm-1, which is in good agreement with Cameron's[6] calculation result. Furthermore, some transitions attributed to the (1,n-2,0)←(0,0,0), n≦6 progressions are first reported, and new parameters are derived from the spectra obtained.     

Li_2H分子电子基态的从头算势能面及其振动激发态

用ab initio MRSDCI/6-311G(2 df,2 Pd)方法研究了Li_2H分子电子基态的势能面,计算了285个几何构型点的势能值,并采用Simons-Parr-Finlan展开式对这些势能值进行了拟合,得到均方差X~2等于4.64×10~(-6)(hartree~2).Li_2H分子电子基态的平衡几何构型为R_e=0.172nm,相似文献   

锗烷(4000)、(3100)、(5000)局域模振动吸收带——强度异常和理论解释

记录了锗烷局域模振动吸收带(4000)、(3100)和(5000)的高分辨光谱,观察到其强度异常现象,并用提出的键耦合模型计算,得到与实验相一致的结论.     

Infrared Spectral Assignment of Pyrimidine and Pyrazine in the CH Stretching Region by an Effective Spectroscopic Hamiltonian

Mid-Infrared spectra of pyrimidine (PM) and pyrazine (PZ) were recorded in the gas phase using a multi-pass long path gas cell. The IR band structure of these compounds above and below 3000 cm⁻¹ is very broad and contains many humps and shoulders. These humps and shoulders are due to various higher quantum excitation of low-frequency vibrational modes, which participate in Fermi resonance with the nearby CH stretch fundamentals and appears in this region. We constructed an Effective Spectroscopic Hamiltonian (ESH) in a mixed local mode (LM) normal mode (NM) basis to assign the various overtone and combination bands in the CH stretching region of these compounds. The CH stretching vibrations of both PZ and PM were treated as symmetrized anharmonic Morse oscillators in local coordinates and the in-plane deformations down to 1000 cm⁻¹ were treated as normal coordinates. The ESHs were diagonalized and the resulting eigenvalues were subsequently fitted in a given parameter space with the experimentally observed bands. The eigenvalues of the converged Hamiltonian are the anharmonic frequencies and the transition intensities were obtained by summing the squared eigenvector components. The overtone and combination transitions near 3000 cm⁻¹ of both PM and PZ were identified and assigned from the eigenvector coefficients of the ESH matrix. The wavefunctions of a pure CH stretch, overtone of the HCC in-plane bend and due to Type 1 Fermi coupling (resonance between a fundamental with an overtones of a low frequency mode, in this case resonance between the CH strech and the overtone of HCC in-plane bending modes) has been demonstrated pictorially.     

The Combustion of SiCl4 in Hot O2/H2 Flames

A simple kinetic model describing the molecular gas phase reactions during the formation of fumed silica (AEROSIL®) was developed. The focus was on the formation of molecular SiO₂, starting from SiCl₄, hydrogen and oxygen. Wherever available, kinetic and thermodynamic parameters were taken from the literature. All other parameters are based on quantum chemical calculations. From these data, an adiabatic model for the combustion reaction has been developed. It was found that a significant amount of molecular SiO₂ forms after about 0.1 and 0.6 ms at starting temperatures between 1000 and 2000 K. The initial reaction of the SiCl₄ combustion in a hydrogen/oxygen flame was found to be different from the combustion in air: The high reactivity of SiCl₄ towards water is favored over the SiCl₄ dissociation, which is the initial and rate‐determining step during the combustion of SiCl₄ in air.     

Chlorine incorporation in silicon films deposited by low-pressure rf discharges in gas mixtures of SiCl4+H2+Ar

Silicon films were deposited from tetrachlorosilane by its dissociation in argon and hydrogen rf plasma at a pressure of 2 Torr. The concentration of chlorine incorporated in the films was found to be dependent on the macrovariables of the plasma such as power input and substrate position in the plasma reactor. Mass spectrometric measurements of the plasma showed that the concentration of HCl in the plasma was strongly dependent on the power input and on position in the plasma along the gas stream. At high input powers the HCl formed in the plasma dissociates to free radicals, contributing to a recombination process in the gas phase and codeposition with silicon on the substrate. The correlation between the HCl reactions in the plasma and the incorporation of Cl in the deposit is shown.Presented in part at the 6th ISPC, Montreal, p. 820.     

催化剂酸碱性对异丙醇脱水活性的影响

研究了具有不同酸碱中心的催化剂对异丙醇脱水反应活性及选择性的影响,结果表明:催化剂表面有合适的酸碱强度和H_0,max值,能引起高的脱水活性和选择性。红外吸附态证实:在接近反应状态下,催化剂表面出现了-CH₂结构吸附,这表明反应物的碱基(OH基)与催化剂表面酸中心作用的同时,酸基(反应物的β-H)与催化剂表面碱作用,催化剂上这种酸碱活性中心协同作用结果使异丙醇脱水生成丙烯的过程很可能以协同机理方式进行。     

The Determination of Impurities in 233UO2 by Spark Source Mass Spectrometry

Abstract

A method for the determination of impurities in ²³³UO₂ has been developed and applied to the analysis of a product stream of ceramic grade ²³³UO₂ powder. The analytical method has combined isotope dilution and internal standard methods to permit the determination of impurities at concentrations between 0.1 and 500 ppm in a single sample.     

The Peroxymonocarbonate Anion HCO4− as an Effective Oxidant in the Gas Phase: A Mass Spectrometric and Theoretical Study on the Reaction with SO2

The peroxymonocarbonate anion, HCO₄⁻, the covalent adduct between the carbon dioxide and hydrogen peroxide anion, effectively reacts with SO₂ in the gas phase following three oxidative routes. Mass spectrometric and electronic structure calculations show that sulphur dioxide is oxidised through a common intermediate to the hydrogen sulphate anion, sulphur trioxide, and sulphur trioxide anion as primary products through formal HO₂⁻, oxygen atom, and oxygen ion transfers. The hydrogen sulphite anion is also formed as a secondary product from the oxygen atom transfer path. The uncommon nucleophilic behaviour of HCO₄⁻ is disclosed by the Lewis acidic properties of SO₂, an amphiphilic molecule that forms intermediates with characteristic and diagnostic geometries with peroxymonocarbonate.     

The Role of Effective Mass of Carrier in the Photocatalytic Behavior of Silver Halide‐Based Ag@AgX (X=Cl,Br, I): A Theoretical Study

The recent discovery of Ag@AgX (X=Cl, Br, I) plasmonic photocatalysts motivates us to elucidate the origin of the higher photocatalytic performance compared to commonly used TiO₂‐based materials. Herein, the electronic structure and effective masses of electrons at the conduction band minimum (CBM) and holes at the valence band maximum (VBM) are studied along different directions in the silver halide for the first time by means of first‐principles calculations. It is revealed that the smaller effective mass of electrons at the CBM in silver halides contributes to the higher photocatalytic performance. The remarkable dependence of the effective mass of holes on the direction and the anion of the silver halide explains well the experimental observed morphology and anion dependence of photocatalytic activities of Ag@AgX. The crystal field splitting of the Ag 4d bands in the valance band of silver halides is found to be a main factor leading to the large effective mass of the photogenerated holes and consequently to a weaker transfer ability. A new crystal design and exerting strain along the coordinate axis are proposed as solutions to decrease the effective mass of holes. The present work may be helpful in exploring this novel class of silver halide‐based photocatalysts.     

2-氨基-5-硝基吡啶在基体辅助激光解吸/电离质谱法测定核酸分子中的应用

报道以2-氨基-5-硝基吡啶为基体用基体辅助激光解吸/电离质谱法(MALDI-MS)对DNA样品进行测定并研究它们的激光质谱特征,结果表明,2-氨基-5-硝基吡啶是DNA的一高效基体.用柠檬酸铵和NH_4~+阳离子交换树脂除去试剂和样品中的碱金属离子,能显著地提高解吸/电离DNA分子的效率.     

高效液相色谱/四极杆-飞行时间质谱测定神经性贝毒

采用高效液相色谱/四极杆 飞行时间质谱(HPLC/Q TOFMS)联用技术对贝类样品中的短裸甲藻毒素 PbTx-2 进行了检测研究。样品经丙酮提取、C18小柱净化后,用Zorbax XDB C18色谱柱(2.1 mm i.d.×150 mm,3.5 μ m)进行分离,流动相为甲醇 水(体积比为85∶15)溶液(含0.5 mmol/L NH4Ac),流速0.20 mL/min 。电喷雾正离子模式,选择质子化PbTx 2分子离子 ［M+H］ +作为前体离子进行TOFMS扫描、测定。结果表明,样品的平均加标