Ar(3P0,2)+NH3初生态产物NH2(2A1)的内态分布

首次报告了在分子束条件下,研究Ar(3P0,2)+NH3碰撞解离反应·利用单光子计数方法进行测量,获得了部分转动分辨的初生态产物NH2(2A1)→（2B1）发射谱,并详细地进行了标识·发现主要为（0,v 2',0)→（0,0,0）跃迁（v2'≤5,K'a≤6,J'≤10)。通过对部分分辨较好的光谱范围进行了模拟,得到反应生成的NH2(2A1,v2'=2,k'a =1)态绕b/c轴的转动温度为1050K,高于母体分子NH3的转动温度300K。由亚稳态碰撞传能电子交换机理认为这是由于碰撞对手Ar和母体NH3分离时反冲作用的结果。碰撞传能解离机理和光解过程不同,后者仅观察到轴的转动激发。     

NH2自由基(A~)2A1,(X~)2B1电子振动能级结构及(A~)2A1～(X~)2B1电子振动跃迁矩的理论计算

利用大振幅弯曲振动哈密顿和矩阵变换方法,考虑Renner-Teller效应 ,计算了NH2自由基(A~)2A1,(X~)2B1态电子弯曲振动和K型转动能级.由计算得到的态函数和基态电偶极矩,计算NH2自由基(A~)2A1～(X~)2B1电子振动相对跃迁矩和电子激发态(A~)2A1的荧光寿命,理论计算结果与实验值符合较好.     

亚稳Ar(~3P_(0.2))原子与NH_3分子碰撞传能分解动力学研究

本文利用流动余辉技术研究了亚稳态Ar(~3P_(0,2))原子与多原子NH_3分子的碰撞传能过程.实验得到了碰撞解离产物NH分子初生态A~3Ⅱ和C~1Ⅱ的振动和转动分布;首次测得了产物分子N_2(C~3Ⅱ_u)的相对振动布居及其生成速率常数.     

氨分子在0_0~0和2_0~1带的选择光离解

本文利用脉冲紫外激光(UV)选择激发氨分子到A~1A″_2电子激发态的两个最低振动能级υ′_2=0和υ′_2=1(ν_2振动),然后检测新生态H原子的飞行谱(TOF),研究了氨分子的光碎片动力学。光谱证实了最近所测的离解能D_0~0(H-NH_2)=4.645eV;绝大多数生成的NH_2(X~2B_1)基处于非振动激发,但是具有围绕a惯性轴的高度转动激发。通过NH_3(A)的υ′_2=1光离解产生的NH_2(X)基具有较高的内部激发,并且显示了在N=K_a转动能级上的反转布居。     

0^3＋与H2碰撞中解离电子俘获过程的全量子计算

利用全量子的分子轨道强耦舍方法。我们研究了基态的O^3（2s^22p^2P）与氢分子碰撞的解南电荷转移过程．分子轨道强耦合计算中采用了自旋耦合价带理论计算的三原子分子势能面和径向耦合矩阵元．对氢分子的自身转动，我们采用无限阶的冲量近似方法，在入射离子能量为0．1 eV／u到500 eV／u的能量区间。我们得到了非解离碰撞过程的振动态选择单电子俘获截面和解离碰撞过程的单电子俘获微分截面，发现解离碰撞截面大约占非解离过程的10％．这表明在实际的应用中。必须包含解离俘获过程的贡献．     

NH4I:Cu2+(Ⅱ4)的混合基态EPR g因子的研究

考虑到NH4I:Cu2+(Ⅱ4)晶体中,Cu2+离子替代NH+4后在第四层邻近体出现一个NH+4空位,以及络离子(CuI6)4-中配体I的价电子有很强的自旋-轨道(SO)耦合相互作用,引进了2B1g态混合进基态2A1g的机制,用双自旋-轨道耦合参数(DSOP)模型和半经验分子轨道法研究了NH4I:Cu2+(Ⅱ4)的EPR g因子.计算结果与实验值符合好,合理地解释了g‖移动Δg‖(=g‖-ge)＞0的疑惑.?     

相对论平均场理论中的张量项对自旋-轨道劈裂的影响

在相对论平均场理论中引入同位旋标量-矢量介子ω张量项, 以²⁰⁸Pb为例,研究了张量项对原子核平均势场、介子场、自旋-轨道耦合势、单粒子能级的自旋-轨道劈裂和原子核壳层结构等的影响.结果发现张量项对核子平均势的影响主要表现在原子核的表面.随着张量耦合强度的增加, 自旋-轨道耦合势增强,单粒子能级的自旋-轨道劈裂增大,从而导致原子核单粒子能级的壳层结构发生很大变化,传统幻数所对应的主壳消失, 新的主壳出现.     

O3+与H2碰撞中解离电子俘获过程的全量子计算

利用全量子的分子轨道强耦合方法,我们研究了基态的O3+(2s22p2P)与氢分子碰撞的解离电荷转移过程.分子轨道强耦合计算中采用了自旋耦合价带理论计算的三原子分子势能面和径向耦合矩阵元.对氢分子的自身转动,我们采用无限阶的冲量近似方法.在入射离子能量为0.1 eV/u到500 eV/u的能量区间,我们得到了非解离碰撞过程的振动态选择单电子俘获截面和解离碰撞过程的单电子俘获微分截面,发现解离碰撞截面大约占非解离过程的10%.这表明在实际的应用中,必须包含解离俘获过程的贡献.     

基于ab initio的BD~+离子激光冷却理论研究

基于相关一致基组aug-cc-pV5Z,采用内收缩多参考组态相互作用方法计算了BD~+离子两个最低解离极限B~+(~1Sg)+D(~2Sg)和B+(~3Pu)+D(~2Sg)对应的5个Λ—S态(X~2Σ~+,A~2Π,B~2Σ+,a~4Π和b~4Σ~+)的势能曲线和跃迁偶极矩.根据计算结果,求解核运动的径向薛定谔方程得到相应电子态的振-转光谱常数、Franck-Condon(F-C)因子和振动能级辐射寿命.其中A~2Π—X~2Σ~+的F-C因子(f_(00)=0.923)、辐射寿命(τ=235 ns)满足激光直接冷却的条件.因此,我们基于分子转动跃迁提出了一个可实现Doppler激光冷却的光循环方案:A~2Π_(1/2)(υ′=0)—X~2Σ+(υ′′=0,1),其中υ′=0中包含2个转动能级,υ′′=0和υ′′=1中分别包含6个和4个转动能级.根据方案,模拟了激光冷却过程中的分子布居数动力学变化过程,并计算了初速度为100 m/s的BD~+,历经5.4 ms散射1150个光子可减速到4.6 m/s、温度为13 mK.     

甲醇气体分子的核自旋变体转换理论研究

按照量子力学中的泡利不相容原理,所有原子核自旋不为零的由相同原子组成的分子都具有不同的原子核自旋变体(简称核自旋变体)。甲醇分子(CH_3OH)则有正甲醇和仲甲醇两种核自旋变体。对此,我们之前以分子的精密激光光谱为手段的实验结果证实了这些核自旋变体存在的真实性。在实现了将它们在空间上的部分分离后,观测到了它们向其自然的热平衡态转化的现象。本研究我们对其可能的转换机制和转换理论进行了解析和数值两方面的分析研究。我们构建了甲醇分子正-仲核自旋变体之间转换过程的理论模型。在推导出核自旋-核自旋以及核自旋-转动相互作用的微扰势能矩阵元后,计算了在低压0.8Torr和300K温度下它们间的相互转换率。计算值1.89×10~(-2) s~(-1)对实验值2.28×10~(-2) s~(-1)的相对误差仅为17%。我们还发现用于计算的五组能级对中贡献最大的两组能级对为(υt K~±,J)=(0 4~-,24)-(0 2,25)和(31~+,34)-(3 0,35)。这里υt是内部转动量子数,量子数K是转动量子数J在甲基CH_3分子轴上的投影分量。     

在小硅化物SiXm（X—H，F，Cl；m＝1─4）中平衡几何和振动频率的从头算研究

本文使用分子轨道从头算方法，在ＨＦ／６—３１Ｇ和ＭＰ２／６—３１Ｇ“水平下，计算了小硅化物ＳｉＸｍ的平衡几何和谐振子振动频率。理论值和实验值的比较表明，对于ＳｉＨｍ分子，实验的键长位于ＨＦ键长和ＭＰ２键长之间，而ＭＰ２振动频率更接近于实验的振动；率。对于ＳｉＣｌｍ分子，无论是键长还是振动频率ＨＦ值和ＭＰ２值都比较接近。对于ＳｉＦｍ分子，处于这两类的中间情况。关联作用随着Ｘ原子的原子序数的增加而减弱。     

Synchrotron radiation VUV double photoionization of some small molecules

The VUV double photoionizations of small molecules (NO,CO,CO2 ,CS2 ,OSC and NH3 ) were investigated with photoionization mass spectroscopy using synchrotron radiation. The double ionization energies of molecules were determined with photoionization efficiency spectroscopy. The total energies of these molecules and their parent dications (NO2+ ,CO2+ ,CO2+2 ,CS2+2 ,OSC2+ and NH2+3 ) were calculated using the Gaussian 03 program and Gaussian 2 calculations. Then,the adiabatic double ionization energies of the molecules were predicated by using high accuracy energy mode. The experimental double ionization energies of these small molecules were all in reasonable agreement with their respective calculated adiabatic double ionization energies. The mechanisms of double photoionization of these molecules were discussed based on a comparison of our experimental results with those predicted theoretically. The equilibrium geometries and harmonic vibrational frequencies of molecules and their parent dications were calculated by using the MP2 (full) method. The differences in configurations between these molecules and their parent dications were also discussed on the basis of theoretical calculations.     

Collisional Energy Transfer from Vibrationally Excited Polyatomic Molecules

Abstract

Intensities and decay rates of delayed fluorescence initiated by CO₂ laser excitation of the triplet-state molecules are used to probe collisional relaxation of vibrationally excited polyatomic molecules. Collisional efficiencies for large polyatomic molecules are found not to exceed the value of 10^?2-10^?3 even in most favourable case of vibrational energy exchange in collisions between parent molecules. At intermediate levels of excitation (1500—12000 cm^?1) the average energies <ΔE> transferred per collision with polyatomic molecules increase as vib>^rn, where m≥2, and decrease with increasing numbers of atoms in the excited molecules.     

Influence of pretreatment methods on adsorption and catalytic characteristics of toluene over heterogeneous palladium based catalysts

The adsorption and catalytic characteristics of heterogeneous palladium based catalyst and its modified catalysts with gases (air and hydrogen) and acidic aqueous solution (HCl) were studied for evaluating the influence of pretreatment methods for toluene. The structural and energetic adsorption properties of the parent and pretreated catalysts were analyzed by means of nitrogen adsorption isotherms and gravimetric methods. The light-off curve and the XPS investigation were used for analyzing the catalytic activity and the surface state of palladium. It was clearly shown from the experimental results that hydrogen pretreated catalysts having metallic surface state exhibited the highest adsorption capacity and catalytic activity compared to that of parent and modified catalysts. The adsorption equilibrium data for toluene were obtained at three different temperatures and correlated successfully with the two-site Langmuir molecular isotherm model (L2m). It was also found that the palladium phase has more adsorption affinity for toluene molecules than the alumina support. The isosteric heat of adsorption calculated by using the Clausius-Clapeyron equation significantly changed with the coverage and the lateral interactions between the adsorbate-adsorbate molecules control the system. Furthermore, comparative analysis of the adsorption energy distribution revealed that the parent and its modified catalysts have different types of surface energetic heterogeneities.     

Hartree-Fock and density functional theory studies on ionization and fragmentation of halomethane molecules by positron impact

The fragmentation patterns of halomethane molecules CF₄, CCl₂F₂, CClF₃ and CHF₃ due to positron impact have been studied by using ab initio and density functional theory (DFT) methods. The geometries of parent molecules and fragments are optimized at HF, MP2 and B3LYP levels of theory using the 6–31+G(d, p) basis set. The calculated reaction energies agree with the experimental values. The condensed Fukui functions have been calculated using the atomic charges of the Mulliken population analysis (MPA) scheme for the halomethane molecules. The calculated condensed Fukui functions successfully predict the reactive site of the halomethane molecules for the positron, electron and radical attacks. The chemical hardness and chemical potential for the above molecules and its fragments are calculated.     

Simulated reaction dynamics of F atoms on partially fluorinated Si(100) surfaces

We have investigated the influence of translational excitation on the reactivity of atomic fluorine with the Si(100) surface via molecular dynamics simulations using a first-principles-derived interaction potential. Surface reactivity is contrasted for both clean and partially fluorinated surfaces with the results of previous simulations of F₂ molecules impinging on Si(100) surfaces, indicating many similarities between the dynamics of F atoms and F₂ molecules. Mechanisms for the reaction are proposed based on reactivity trends and scattered product energy and angular distributions, including evidence for the existence of a precursor-mediated adsorption pathway for low incident energy F atoms on partially fluorinated surfaces.     

Experimental investigation of ultracold atom-molecule collisions

Ultracold collisions between Cs atoms and Cs2 dimers in the electronic ground state are observed in an optically trapped gas of atoms and molecules. The Cs2 molecules are formed in the triplet ground state by cw photoassociation through the outer well of the 0-(g) (P3/2) excited electronic state. Inelastic atom-molecule collisions converting internal excitation into kinetic energy lead to a loss of Cs2 molecules from the dipole trap. Rate coefficients are determined for collisions involving Cs atoms in either the F=3 or F=4 hyperfine ground state, and Cs2 molecules in either highly vibrationally excited states (nu'=32-47) or in low vibrational states (nu'=4-6) of the a3 summation(u)+ triplet ground state. The rate coefficients beta approximately 10(-10) cm3/s are found to be largely independent of the vibrational and rotational excitation indicating unitary limited cross sections.     

Control of reactive plasmas for low-k/Cu integration

We proposed models for controlling surface reactions during etching of SiOCH and organic material. The etch rate of each material can be determined by the balance between the total atom fluxes of O, C, F, N, and H that were supplied from both the plasma and the etched material to the reactive layer. Low-k films (SiOCH, porous SiOCH, and organic material) have narrow process windows for obtaining good etching properties, such as selectivity, because the polymer and reactive layers on these films can be changed by only slight changes in the plasma parameters. Therefore, the partial pressure and dissociation of parent gas molecules in fluorocarbon or N-H plasma as well as plasma-wall interaction must be controlled. To create highly reliable interconnects, the interfaces between the metal and low-k must be optimized during the etching of stopper material and ashing. The surface of Cu is very reactive, the remaining F induces degradation of Cu. SiOCH can easily be oxidized during ashing processes, and the adsorption of H₂O on damaged SiOCH causes interconnect failure during electrical tests. To suppress problems in the etching and ashing processes, the balance of the total atom fluxes should be quantitatively and instantaneously controlled to the optimum point for each material.     

Ratiometric comparison of intense field ionization of atoms and diatomic molecules

Intense-laser ionization rates for rare gas atoms and diatomic molecules have been precisely compared by making simultaneous measurements of ionization yield vs laser intensity for mixed atomic and molecular targets. At a given laser intensity, the N (2) and F (2) ionization yields are slightly greater than that of Ar. Conversely, comparison of O (2) and S (2) with Xe indicates significant ionization suppression in these molecules. Recent molecular ionization models that successfully describe ionization suppression in O (2) and its absence in N (2) fail to explain our observations in F (2) and S (2).     

基态原子与理想金属Au表面间的范德瓦尔斯作用

研究了基态碱金属原子与理想金属Au表面间的范德瓦尔斯(vdW)作用.通过分析电四极跃迁对vdW的贡献,构建了计算超精细能级碱金属原子与理想金属表面间vdW作用系数C3的理论模型.以85Rb、133Cs为例,计算了其基态原子超精细能级的C3系数.其中85Rb: 52S1/2 (F=2)及52S1/2 (F=3)对应的C3系数分别为:2.2409 及2.2425 ;133Cs: 62S1/2 (F=3)及62S1/2 (F=4)分别对应 2.4480 及2.4538 .研究还发现随着 的增大,C3增大,z (原子与金属表面之间的距离)不变时,原子与理想金属表面间vdW作用增强. 这一研究在实现原子囚禁及介质表面量子反射等方面具有重要意义