高离化态Cu18+离子的双电子复合及共振转移激发过程的理论研究

在准相对论理论框架下计算了Cu¹⁸⁺离子的双电子复合截面，分析了组态相互作用对截面的影响.基于这些数据，在冲量近似下，通过对靶原子中电子动量分布的卷积，进一步得到了Cu¹⁸⁺与H₂碰撞过程中的共振转移激发截面，并与已有的实验结果作了比较，符合得很好.A 关键词： 双电子复合 共振转移激发     

类钠Ni~(17+)离子双电子复合过程理论研究

使用基于相对论多组态方法的FAC程序,研究了类钠Ni17+(3s)离子通过双激发态Ni16+(3pnl,3dnl)(Δn=0激发)的双电子复合过程,得到了态选择的双电子复合截面和速率系数,并与文献中的实验和理论数据进行了对比.结果发现,计算通过3p3/210l和3p1/211l共振态的双电子复合积分截面在实验误差范围内与实验测量很好地符合,并好于全相对论的多体微扰理论计算结果.结合量子亏损理论,发现包含高里德伯态的共振双激发态的辐射跃迁和自电离速率具有较好的标度关系,利用该关系给出了近激发阈值的所有共振态的双电子复合积分截面和速率系数.比较3pnl和3dnl两个系列,发现在低温(大约小于100eV)等离子体情况下前者速率系数比后者大,更高的温度后者大.     

Adiabatic Hyperspherical Approach to the Problems of Muon Catalyzed Fusion

The adiabatic hyperspherical approach (AHSA) is applied for the numerical investigation of the scattering processes and resonances in Coulomb three-body mesic atomic systems. The results of the calculations of elastic and inelastic cross sections in low-energy collisions aμ + b (a, b = p, d, t), energies, lifetimes and local characteristics of resonant states of mesic molecular ions ⁿ Heaμ⁺ (n = 3, 4) are presented. This revised version was published online in August 2006 with corrections to the Cover Date.     

Calculation of dielectronic recombination cross sections and rate coefficients for heliumlike carbon

A simplified relativistic configuration interaction method is used to calculate the dielectronic recombination cross sections and rate coefficients for heliumlike carbon. In this method, the infinite resonant doubly excited states can be treated conveniently in the frame of Quantum Defect Theory. Our calculated cross sections are in agreements with the experimental measurements except for the 1s2lnl'(n=6,7) resonances. The total energy-integrated cross sections and rate coefficients over all dielectronic resonances are in agreements with the experimental measurements within percent. Received: 7 July 1997 / Revised: 7 October 1997 / Accepted: 8 December 1997     

Positron scattering from hydrocarbons

The total cross sections for positron impact on hydrocarbons have been calculated using the additivity rule in which the total cross section for a molecule is the sum of the total cross section for the constituent atoms. The energy range considered is from a few eV to several thousand eV. The total cross sections for positron impact on an atom are calculated by employing a complex spherical potential which comprises of a static, polarization and an absorption potential. We have good agreement with the experimental results for hydrocarbons for positron energy ⩾100 eV. Our results also agree with the available calculations for CH₄ and C₂H₂ which employed full molecular wavefunctions beyond 100 eV. Our absorption cross sections also agree with molecular wave-function calculations for C₂H₂ and CH₄ beyond 100 eV. We have shown the Bethe plots fore ⁺−C ande ⁺−H scattering systems and Bethe parameters have been extracted. We have fitted the cross section for positron impact on hydrocarbons in the formσ _t(C _n H _m )=naE ⁻ b+mcE ⁻ d in the energy range 300–5000 eV wherea=195.0543,b=0.7986,c=371.1757 andd=1.1379 withE in eV andσ _t in 10⁻¹⁶ cm².     

Positron and electron scattering on atoms and molecules–modified effective range theory revisited

New experiments on the very low-energy electron and positron scattering allow to verify the old question on applicability of modified effective range theory (MERT). We perform it using an analytical solution of the Schrödinger equation with the long-range polarization potential. In this work two atomic (He, Ar) and molecular (H₂, CH₄) target are studied using this approach. Total cross sections were used for obtaining parameters characterizing the scattering phase shifts related to the short-range interaction potential; differential cross sections were used for comparison. Differently from previous works, we conclude that MERT with few (2-3) partial waves applies very well up to energies of few eV in all four targets studied. For positrons, reliable experimental data indicate occurrence of zeros in the s-wave phase shifts for all four targets. This should be recognized as Ramsauer-Townsend minima.     

三甲基镓在Pd(111)表面吸附解离及表面预吸附H和O的影响

利用X-射线光电子能谱（XPS）和程序升温脱附谱（TPD）研究了三甲基镓在Pd（111）表面的吸附和解离行为,并考察了表面预吸附H和O的影响。结果表明,在吸附温度为140 K时,三甲基镓在Pd（111）上主要为解离吸附,此时表面物种为Ga（CH₃）_x （x=1,2,3）和CH_x物种。加热将导致Ga的甲基化合物中的Ga-C键发生分步断裂,在不同温度下产生CH₄和H₂从表面脱附。同时,XPS结果证实了在275~325 K的温度区间内存在Ga甲基化合物的分子脱附。退火至更高温度,表面只观察到积碳和金属Ga物种,这二者随着温度的继续升高逐渐向体相扩散。在Pd（111）表面预吸附O和H对上述吸附和解离行为存在显著的影响。当表面预吸附H时,脱附产物CH₄和H₂的脱附主要位于315 K,可归属为一甲基镓的解离脱附。当表面预吸附O时,只在258 K观察到CH₄和H₂的脱附峰,可能来自于Pd-O-Ga（CH₃）₂吸附结构的解离.     

Electron impact total cross section calculations for CH3SH (methanethiol) from threshold to 5 keV

We report calculated total elastic cross sections Q_el, total ionisation cross sections, Q_ion, summed total excitation cross sections ∑Q_exc and total cross sections Q_T for CH₃SH upon electron impact for energies from ionisation threshold to 5 keV. We have employed Spherical Complex Optical Potential (SCOP) formalism to calculate total elastic cross section Q_el, and total inelastic cross section Q_inel and used Complex Scattering Potential – the ionisation contribution (CSP-ic) method to extract the ionisation cross sections, Q_ion, from the calculated Q_inel. The calculated total cross sections are examined as functions of incident electron energy and are compared with available data wherever possible and overall good agreement is observed. In this work Q_el, Q_ion, and ∑Q_exc are reported for the first time for CH₃SH in this energy range.     

Quantum rotational scattering of H2 and its isotopologues with He

Quantum close-coupling computations of the rotational quenching of H₂ and its isotopologues due to He impact are performed using a highly accurate potential energy surface. State-to-state cross sections are obtained in a wide range of collision energies between 10^?5 cm^?1 and 10⁴ cm^?1, and the theoretical rate coefficients are reported for temperatures ranging from 10^?4 K to 3000 K. Compared with previous studies, the well depth of the potential adopted in this study is larger, leading to stronger resonance effects in the cross sections of He-HD. The accurate potential was employed to investigate the isotope effects of H₂ in detail. The cross-section resonances shift towards lower collision energies and become stronger with increasing reduced mass. The calculated cross sections and rate coefficients of H₂ and its isotopic variants in collisions with He are provided to study the energy transfer in these systems.     

The absorption cross sections of N2, O2, CO,NO, CO2, N2O,CH4, C2H4, C2H6 and C4H10 from 180 to 700Å

The absorption cross sections of N₂, O₂, CO, NO, CO₂, N₂O, CH₄, C₂H₄, C₂H₆, C₄H₁₀ have been measured photoelectrically in the 180–700 Å region using synchrotron radiation. The absorption cross sections in the region λ ≥ 500 Å was found to be structureless and to increase monotonically with wavelength for all gases. The positions of the structure observed in the 520–720 Å region for N₂, O₂, CO₂ and N₂O are consistent with the various Rydberg series reported by previous authors.     

H1+,H2+,H3+和He,Ne,Ar碰撞过程中的巴耳末系Hα,Hβ,Hγ发射

实验利用TN-1710光学多道分析系统(OMA),对H₁⁺,H₂⁺,H₃⁺和He,Ne,Ar碰撞过程中产生的巴耳末系H_α,H_β,H_γ发射进行了测量,入射离子H₁⁺,H₂⁺,H₃⁺的 关键词：     

Geometric shielding corrections for total cross section calculations of electron scattering by CH4, C2H6, C2H3F3, C2H4, C2F4, C2Cl4 and C2Cl2F2 from 30–5000?eV

To quantify the changes in the geometric shielding effect in a molecule as the incident electron energy varies, an empirical fraction, which represents the total cross section contributions of shielded atoms in a molecule at different energies, is presented. Using this empirical fraction, the total cross sections for electron scattering by CH₄, C₂H₆, C₂H₃F₃, C₂H₄, C₂F₄, C₂Cl₄ and C₂Cl₂F₂ are calculated over a wide energy range from 30 to 5000 eV by the additivity rule model at the Hartree-Fock level. The quantitative total cross sections are compared with those obtained by experiment and other theories where available. Good agreement is attained above 100 eV.     

The effect of temperature on collision induced intersystem crossing in the reaction of CH2 with H2

Laser flash photolysis of ketene at 308 nm, coupled with H atom vacuum ultraviolet laser induced fluorescence, was used to determine the branching ratio for the CH₃ + H channel (1a) in the reaction of CH₂¹A₁ (¹CH₂) with H₂, over the temperature range 300–500 K. This reaction channel competes with collision induced intersystem crossing (CIISC) to form triplet methylene, CH₂³B₁ (³CH₂) (channel 1b). The branching ratio for H formation, k_1a/k₁, was determined by measuring the relative H atom yield in three time resolved measurements of H: (i) in ketene, H₂ mixtures, where H is exclusively formed by reaction 1a, (ii) in ketene, H₂, NO mixtures ([NO] [H₂]), where H is formed at short times by 1a and at longer times by ³CH₂ + NO, following 1b, and (iii) in ketene, He, NO mixtures ([NO] [He]), where H is exclusively formed from ³CH₂ + NO, following deactivation of singlet to triplet methylene by He. k_1a/k₁ was found to increase from 0.85 at 300 K to unity at 500 K, with the yield of CIISC decreasing from 0.15 to zero. This is the first measurement of the temperature dependence of the rate coefficient for CIISC in a reactive system. The rate coefficient for CIISC with an inert gas increases with T. It has been suggested that the fractional yield of CIISC will increase with temperature in reactive systems, thus reducing the rate coefficient for reaction at high temperature, with significant consequences for combustion systems. The present experiments demonstrate that this is not the case for reaction with H₂ and implies a different CIISC mechanism for reactive vs inert collision partners.     

Catalytic effect of water,water dimer,water trimer,HCOOH, H2SO4, CH3CH2COOH and HN(NO2)2 on the isomerisation of HN(NO2)2 to O2NNN(O)OH: a mechanism study

In this article, the isomerisation mechanisms of HN(NO₂)₂ to O₂NNN(O)OH without and with catalyst X (X = H₂O, (H₂O)₂, (H₂O)₃, HCOOH, H₂SO₄, CH₃CH₂COOH and HN(NO₂)₂) have been investigated theoretically at the CBS-QB3 level of theory. Our results show that the catalyst X (X = H₂O, (H₂O)₂, (H₂O)₃, HCOOH, H₂SO₄ and CH₃CH₂COOH) shows different positive catalytic effects on reducing the apparent activation energy of the isomerisation reaction processes. Such different catalytic effects are mainly related to the number of hydrogen bonds and the size of the ring structure in X (X = H₂O, (H₂O)₂ and (H₂O)₃)-assisted transition states, as well as different values of pK_a for H₂SO₄, HCOOH and CH₃CH₂COOH. Very interesting is also the fact that H₂SO₄-assisted reaction is the most favourable for the hydrogen transfer from HN(NO₂)₂ to O₂NNN(O)OH, due to the smallest pK_a (?3.0) value of H₂SO₄ than H₂O, HCOOH, H₂SO₄ and CH₃CH₂COOH, and also because of the largest ∠X???H???Y (the angle between the hydrogen bond donor and acceptor) involved in H₂SO₄-assisted transition state. Compared to the self-catalysis of the isomerisation mechanisms of HN(NO₂)₂ to O₂NNN(O)OH, the apparent activation energy of H₂SO₄-assisted channel also reduces by 9.6 kcal?mol^?1, indicating that H₂SO₄ can affect the isomerisation of HN(NO₂)₂ to O₂NNN(O)OH, most obvious among all the catalysts H₂O, (H₂O)₂, (H₂O)₃, HCOOH, H₂SO₄, CH₃CH₂COOH and HN(NO₂)₂.     

O3+与H2碰撞中非解离电荷转移过程的全量子计算

应用全量子的分子轨道强耦合方法,研究了基态的O³⁺(2s²2p ²P)与氢分子碰撞的非解离电荷转移过程,计算了不同方位角(25°,45°,89°),能量分别为100,500,1000和5000eV/u时的单电子俘获的振动分辨的态选择截面及相应的微分截面.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,采用无限阶的冲量近似方法;对体系的电子运动同H₂或H^{+< 关键词： 非解离电荷转移过程 全量子的分子轨道强耦合方法 无限阶冲量近似 振动冲量近似国家自然科学基金(批准号：10604011 10574020)和国家高技术研究发展计划(863)惯性约束聚变领域资助的课题.}     

SiC外延层表面化学态的研究

用高分辨X射线光电子能谱仪(XPS)和傅里叶变换红外(FTIR)光谱仪研究了SiC外延层表面的组分结构. XPS宽扫描谱,红外掠反射吸收谱及红外镜面反射谱的解析结果说明SiC外延层表面是由Si—O—Si和Si—CH₂—Si聚合体构成的非晶SiC_xO_y:H. SiC外延层表面的化学态结构为Si(CH₂)₄,SiO(CH₂)₃,SiO₂(CH₃)₂,SiO₃(CH₃),Si—Si,游离H₂O,缔合OH,Si—OH,O和O₂. 根据化学态结构和元素电负性确定了化学态的各原子芯电子束缚能顺序,并与XPS窄扫描谱拟合结果相对比,建立了化学态与其束缚能的对应关系,进而用Si(CH₂)₄的实际C 1s束缚能值进行校正,确定了各化学态的束缚能. 结果发现,除了SiC_xO_y(x=1,2,3,4,x+y=4)的Si 2p束缚能彼此不同外,其C 1s和O 1s彼此也不相同,其中SiO₂(CH₃)₂和SiO₃(CH₃)的C 1s束缚能与CH_m和C—O中C 1s的相近,对此从化学态结构,元素电负性和邻位效应进行了解释. 关键词： SiC 化学态 XPS FTIR     

Total ionisation cross sections for chlorofluoromethanes and CClx radicals by electron impact

We report here the total ionisation cross section for chlorofluoromethanes, namely CCl₃F (Freon 11), CCl₂F₂ (Freon 12), CClF₃ (Freon 13), CHCl₂F (Freon 21), CHClF₂ (Freon 22), CH₂ClF (Freon 31), CCl₄ and CCl_x (x = 1–3), radicals by electron impact from ionisation threshold to 2 keV. The total inelastic cross section is obtained employing a complex optical potential formalism and solving the Schrödinger equation through partial wave analysis. Using the complex scattering potential-ionisation contribution method, the total ionisation cross section is derived from the inelastic cross section for these targets. The results obtained are then compared with the existing experimental and theoretical data, wherever available. The present result shows reasonable agreement with previous data. For the CCl_x radicals, the ionisation cross section is predicted for the first time. The data reported here have immense interest to atmospheric and technological plasma modelling.     

New data for the 197Au(γ, nX) and 197Au(γ, 2nX) reaction cross sections

The results from experimental and theoretical studies of the total and partial cross sections of photoneutron reactions on the ¹⁹⁷Au isotope were analyzed. The cross sections for reactions σ(γ, nX) = σ(γ, n) + σ(γ, np) + … + σ(γ, 2nX) = σ(γ, 2n) + σ(γ, 2np) + … were evaluated in the energy range 7 ≤ E _γ ≤ 30 MeV using an approach free of the shortcomings of experimental photoneutron multiplicity sorting methods. The total photoneutron reaction cross sections σ^exp(γ, xn) = σ^exp(γ, nX) + 2σ^exp(γ, 2nX) + … = σ^exp(γ, n) + σ^exp(γ, np) + 2σ^exp(γ, 2n) + 2σ^exp(γ, 2np) + … were used as the initial experimental data. The contributions from the cross sections σ(γ, nX) and σ(γ, 2nX) to the cross sections σ^exp(γ, xn) were separated using the multiplicity transition functions F ₁ ^theor = σ^theor(γ, 1nX)/σ^theor(γ, xn) and F ₂ ^theor = σ^theor(γ, 2nX)/σ^theor(γ, xn), calculated within an updated version of the pre-equilibrium model of photonuclear reactions. New evaluated data for both partial reaction cross sections, i.e., σ^eval (γ, 1nX) = F ₁ ^theorσ^exp(γ, xn) and σ^eval(γ, 2nX) = F ₂ ^theorσ^exp(γ, xn), were obtained. The cross sections σeval(γ, nX) and σ^eval.(γ, 2nX) evaluated using the theoretically calculated functions F _1,2^theor are consistent with the Livermore data, but substantially contradict the Saclay data.     

Molekularstrahlmessungen von Stoßquerschnitten für Übergänge zwischen definierten Rotationszuständen zwei-atomiger Moleküle

Inelastic collision cross sections for transitions between specified rotational states designated by (J, M) have been measured in a molecular beam apparatus. With an electrostatic four pole field molecules in a specified rotational state are separated out of a molecular beam and focussed into a gas filled scattering chamber. Molecules which have been scattered by less than 1/2° are then collected in a second four pole field, located directly behind the scattering chamber, and are analyzed for their rotational state. From a comparison of the measured pressure dependence with calculated curves a determination of inelastic collision cross sections for specified quantum jumps is possible. Measured inelastic scattering cross sections for the transitions (2,0→3,0) are reported for the gases He, Ne, Ar, Kr, CH₄, SF₆, H₂, O₂, Air, N₂O, H₂O, CF₂Cl₂. The values range between about 5 and 100 Ų in the order indicated. The scattering gases NH₃ und ND₃ yielded larger cross sections of about 600 Ų and, in addition, the transitions (3,0)→(2,0),(1,0)→(2,0), (2,0)→(1,0) and (3,0)→(1,0) were observed. Total cross sections for the same gases were also measured with the apparatus.     

ESR spectroscopics study of radicals formed from methoxycarbonylcholine picrate hemihydrate

Abstract

The electron spin resonance of γ-irradiated single crystals of methoxycarbonylcholine picrate hemihydrate, C₇H₁₆NO₃ ⁺ · C₆H₂N₃O₇ ^? · ½ H₂O has been observed and analyzed for different orientations of the crystal in the magnetic field. The crystals have been investigated between 70 and 350 K. The spectra were found to be temperature independent and the radiation damage centers are attributed to – ?[Obar]OCH₃ and –CH₂CH₂O? radicals. The g and hyperfine coupling constants were found to be almost isotropic with an average, g = 2.0060, a _H1 = 4.4G for –CH₂CH₂O?, g = 2.0050, a _H2 = 3.5G for –CH₂CH₂O? and g = 2.0045, a _H = 3.5 G for –?[Obar]OCH₃. These values indicate a long-range coupling between the unpaired electron and H protons.