甲烷分子电子碰撞电离和解离的实验研究

本文利用反应显微成像技术(reaction microscope)研究了54 eV电子入射甲烷分子导致的电离解离过程,详细分析了电离解离产生的CH⁺₂,CH⁺,C⁺离子碎片的动能分布情况.实验结果表明,该入射能量下产生CH⁺₂,CH⁺,C⁺离子碎片主要贡献来自2a₁内价轨道电子的直接电离过程产生的离子态(2a< 关键词： 反应显微成像谱仪 电离解离 能量沉积 动能分布     

关於展开子

本文讨论展开子的一些性质。将展开子A_nrst变换至ξ表示,定义为〈ξ|〉=∑ξ₀^-n-1ξ₁^rξ₂^sξ₃^tA_nrst,立即可以看出〈ξ|〉在洛伦兹变换中的变换,正如标准表示中的变换。由此可以立即证明,在标志洛伦兹群的各种不可约表示的两个量J=-1/2I_klI^kl,I=1/2ε^klmnI_klI_mn中,对於展开子而言,I一定等於零。我们也证明了如果我们要求J的本徵函数〈ξ|〉在各处行为正常,便获得J<0,亦即展开子表示为么正的条件。对於在展开子空间(J,0)及其他空间(I′,J′)中作用的矢量算符,我们作出了计算。选择定则为(i)I′=0,J′=1+J±2(1+J)^1/2;(ii)I′=±(1+J)^1/2i,J′=1+J。我们又证明了ξ^vξ_v?/(?ξ^μ)/(ξ^μ)-(1±(1+J)^1/2)ξ_μ将(J,0)空间变为(1+J±2(1+J)^1/2,0)空间。利用上式中取“-”符号的算符,我们可以构成一个像(-ir_μp^μ+k)ψ=0的波动方程,其中ψ只在两个展开子空间中。     

Luminescence spectroscopy of high-energy 4f 11 levels of Er3+ in fluorides

The 4f¹¹ energy levels of Er³⁺ in LiYF₄ in the spectral region 39000–65000 cm^?1 have been studied. The agreement between experimental energy levels, obtained from luminescence excitation spectra, and calculated energy levels is good. Luminescence originating from high-lying energy levels has been investigated. Emission from the states ⁴D_1/2 (～47 200cm^?1), ²F(2)_7/2 (～54700cm^?1) and ²F(2)_5/2 (～63 300cm^?1) is observed. ²F(2)_5/2 emission occurs for Er³⁺ in LaF₃, where the ²F(2)_5/2 level is situated just below the lowest 4f¹⁰5d state, but also for Er³⁺ in LiYF₄, where it lies in between the two lowest 4f¹⁰5d states.     

Feasibility Study on Quantitative Measurements of Singlet Oxygen Generation Using Singlet Oxygen Sensor Green

The purpose of this study is to investigate the feasibility for quantitative measurement of singlet oxygen (¹O₂) generation by using a newly developed ¹O₂-specific fluorescence probe Singlet Oxygen Sensor Green reagent (SOSG). ¹O₂ generation from photoirradiation of a model photosensitizer Rose Bengal (RB), in initially air-statured phosphate buffered saline (PBS) was indirectly monitored with SOSG. In the presence of ¹O₂, SOSG can react with ¹O₂ to produce SOSG endoperoxides (SOSG-EP) that emit strong green fluorescence with the maximum at 531 nm. The green fluorescence of SOSG-EP is mainly dependent on the initial concentrations of RB and SOSG, and the photoirradiation time for ¹O₂ generation. Furthermore, kinetic analysis of the RB-sensitized photooxidation of SOSG is performed that, for the first time, allows quantitative measurement of ¹O₂ generation directly from the determination of reaction rate. In addition, the obtained ¹O₂ quantum yield of porphyrin-based photosensitizer hematoporphyrin monomethyl ether (HMME) in PBS by using SOSG is in good agreement with the value that independently determined by using direct measurement of ¹O₂ luminescence. The results of this study clearly demonstrate that the quantitative measurement of ¹O₂ generation using SOSG can be achieved by determining the reaction rate with an appropriate measurement protocol.     

Optical absorption and EPR studies on enargite

The behaviour of transition metal ions in enargite has been studied by electron paramagnetic resonance and absorption spectroscopy in the UV–VIS and near-IR regions. The ground state of Cu(II) ions in enargite is confirmed as ²B_1g since g₁₁>g_⊥ (2.54>2.11). Three characteristic bands observed in the optical absorption spectra at 8275, 13105 and 18420 cm^?1 are assigned to the transitions, ²B_1g→²A_1g, ²B_1g→²B₂ and ²B_1g→²E_g, respectively, of Cu(II) ion in the tetragonal field. The presence of Fe(II) bands is an evidence for iron impurities in the mineral.     

Tautomery and acid-base properties of some azoderivatives of benzoylacetone

The structural, tautomeric and acid-base properties of the new 1-phenyl-2-(2-hydroxy-3-sulfo-5-chlorophenylhydrazo)butane-1,3-dione (H₂L¹), 1-phenyl-2-(2-hydroxy-3,5-disulfophenylhydrazo)butane-1,3-dione (H₂L²), 1-phenyl-2-(2-hydroxy-3-sulfo-5-nitrophenylhydrazo)butane-1,3-dione (H₂L³) and 1-phenyl-2-(2-hydroxy-4-nitrophenylhydrazo)butane-1,3-dione (H₂L⁴) were studied using IR, ¹H and ¹³C NMR spectroscopies and potentiometry. The study reveals that H₂L^1-4 and the known 1-phenyl-2-(2-hydroxyphenylhydrazo)butane-1,3-dione (H₂L⁵) exist in solution as a mixture of Z-enol-azo-II and hydrazo-III tautomeric forms and that an increase in the solvent polarity shifts the tautomeric balance to the enol-azo form. The thermodynamic parameters of the proton dissociation in H₂L^1-5 were determined showing that this process is unspontaneous, endothermic and entropically unfavorable.     

新型激光晶体Yb:KY(WO4)2的结构与光谱

采用顶部籽晶提拉法，以K₂W₂O₇为助溶剂，生长了Yb:KY(WO₄)₂新型激光晶体.经热重-差热分析，确定晶体熔点为1045℃，相变温度为1010℃.X射线粉末衍射测试，验证所生长的晶体为β-Yb:KY(WO₄)₂.晶体结构分析确定Yb:KY(WO₄)₂晶体由WO₆八面体连接而成，WO₆八面体是由双氧桥(WOOW)及单氧桥(WOW)构成.晶体粉末样品室温下的红外及拉曼光谱测试，确定WO₆原子基团、双氧桥及单氧桥的振动频率.晶体的吸收峰位于940nm，980nm，发射峰位于989nm—1030nm. 关键词： 晶体结构 光谱 晶体生长     

正偏离Bragg定律的二元化合物靶中离子射程参数研究

研究了正偏离Bragg定律,即计算S_e(E)值高于实测S_e(E)的二元系化合物靶的离子射程特性。文中应用“regular”观点引入了“双原子模型”,在二元化合物靶的射程计算中,不仅考虑相同“原子对”对离子的阻止本领S₁₁(E),S₂₂(E),而且考虑不同“原子对”对离子的阻止本领S₁₂(E),S₂₁(E)。文中还应用Berthelot关系,使S₁₂(E)=S₂₁(E)=(S₁₁(E)·S₂₂(E))^1/2,则二元系靶的阻止本领及总的射程为NS(E)=1/2[(N₁S₁₁(E))^1/2+(N₂S₂₂(E)^1/2)]², R=4/a[x-A₁(arctg(2x+f)/△^1/2-arctg(f/△^1/2))-B₁(ln(x+g)²/g²·e/(x²+fx+e)) -b/2 ln(x²+fx+e/e)。这里X=E^1/2,E为离子注入能量,所有其它常数是与离子和靶的质量、原子序数有关的常数。结合文献[1]提出的R与R_p,R_p与△R_p的关系式,可计算得正偏离系统的投影射程R_p及其偏差量△R_p。并对各关系式的物理意义作了阐明。 关键词：     

Transformation of Fe(II)-Fe(III) Hydroxysulphite into Hydroxysulphate Green Rusts

Fe(II)-Fe(III) hydroxysulphite Green Rust 1, GR1(SO₃ ^2?), can be obtained by oxidation of Fe(OH)₂ precipitates in aqueous solution and characterised by X-ray diffraction and Mössbauer spectroscopy. In contrast to other Green Rusts (GRs) which then oxidise directly into ferric oxyhydroxides and magnetite, GR1(SO₃ ^2?) first oxidises into a Green Rust two compound, as identified by X-ray diffraction. Mössbauer analysis reveals that this GR2 is the Fe(II)-Fe(III) hydroxysulphate, GR2(SO₄ ^2?). Such an oxidation process, GR1(SO₃ ^2?) → GR2(SO₄ ^2?) confirms that the average oxidation number of Fe increases according to the chemical formulae previously proposed, [Fe^II ₆Fe^III ₂(OH)₁₆]²⁺[SO₃ · mH₂O]^2?, and [Fe^II ₄Fe^III ₂(OH)₁₂]²⁺[SO₄ · nH₂O]^2? for GR1(SO₃ ^2?) and GR2(SO₄ ^2?) with oxidation numbers of 2.25 and 2.33, respectively. The process implies likely the presence of sulphate ions inherent to the oxidation of sulphite in the solution.     

Si中S0对、Se0对和Te0对的电子结构

利用紧束缚近似下的格林函数方法,讨论了Si中(S⁰)₂,(Se⁰)₂及(Te⁰)₂基态的能级和波函数。分析了几种不同的观点。(S⁰)₂,(Se⁰)₂及(Te⁰)₂均在禁带中引入一个对称性的A_1g能级和一个反对称性的A_2u能级,二者都是填满的。现有实验观测到的是较高的A_1g能级。从理论上指出了对称性的A_1g能级反而高于反对称性的能级的原因。而Si中(Se₂)⁺的g因子测量值和(S₂)⁺,(Se₂)⁺的ESR实验结果也支持本文的观点。 关键词：     

有重位点阵关系两相的复合点阵(Ⅱ)——两相空间点阵及其点阵平面的重合系数

本文用数论分析方法,给出有重位点阵关系两相空间点阵及其点阵平面重合系数求法的普遍而简便的公式。空间点阵的重合系数α₂⁽³⁾=1/|C⁽¹⁾|,点阵平面的重合系数α₂^(h)= (H⁽²⁾C⁽¹⁾/|C⁽¹⁾|, C⁽¹⁾为重位点阵基矢对应矩阵,H⁽²⁾=[h₁⁽²⁾h₂⁽²⁾h₃⁽²⁾].在C⁽¹⁾未知的情况下,空间点阵及其点阵平面的重合系数可以通过两相基矢有理对应矩阵φ及重合系数矩阵C来求,这时α₂⁽³⁾= k₁⁽²⁾k₂⁽²⁾/d³, α₂^(h)=(CH⁽²⁾,dk₁⁽²⁾)/d².求矩阵C比求矩阵C⁽¹⁾要方便得多。 关键词：     

Raman spectroscopic study of the multi‐anion uranyl mineral schroeckingerite

Raman spectroscopy complemented with infrared (IR) spectroscopy has been used to study the mineral schroeckingerite. The mineral is a multi‐anion mineral and has (UO₂)²⁺, (SO₄)²⁻ and (CO₃)²⁻ units in its structure, and bands attributed to these vibrating units are readily identified in the Raman spectra. Symmetric stretching modes at 815, 983 and 1092 cm⁻¹ are assigned to (UO₂)²⁺, (SO₄)²⁻ and (CO₃)²⁻ units, respectively. The antisymmetric stretching modes of (UO₂)²⁺, (SO₄)²⁻ are not observed in the Raman spectra but may be readily observed in the IR spectrum at 898 and 1180 cm⁻¹. The antisymmetric stretching mode of (CO₃)²⁻ is observed in the Raman spectrum at 1374 cm⁻¹, as is also the ν₄ (CO₃)²⁻ bending modes at 742 and 707 cm⁻¹. No ν₂ (CO₃)²⁻ bending modes are observed in the Raman spectrum of schroeckingerite. All the spectroscopic evidence points to a highly ordered structure of this mineral. Copyright © 2007 John Wiley & Sons, Ltd.     

Chaos and curvature in a quartic Hamiltonian system

Chaotic behaviour of a quartic oscillator system given byH l/2(p ₁ ² +p ₂ ² )+ (1/12)(1 -α) (q ₁ ⁴ +q ₂ ⁴ )+1/2q ₁ ² q ₂ ² is studied. Though the Riemannian curvature is positive the system is nonintegrable except when S/B α = 0. Calculation of maximal Lyapunov exponents indicates a direct correlation between chaos and negative curvature of the potential boundary.     

Ion-molecular interactions in solutions of methanesulfonic acid in diethylamine according to IR spectroscopy data

The methanesulfonic acid (MSA)-diethylamine (DEA) binary liquid system is studied over the entire range of compositions at 30°C by using multiple frustrated total internal reflection IR spectroscopy. Solutions with acid: base equimolar ratio contain only 1 : 1 ion pairs. Upon adding the acid, a MSA molecule abstracts an anion from the 1 : 1 complex to produce a protonated DEA and an (H₃C(O₂)SO…H…OS(O₂)CH₃)⁻ anion with a strong H bond: (C₂H₅)₂(H)NH⁺ · OS(O₂)CH₃⁻ + HOS(O₂)CH₃ ↔ (C₂H₅)₂(H)NH⁺ + (H₃C(O₂)SO…H…OS(O₂)CH₃)⁻. This equilibrium is shifted to the left. The 1 : 1 complex is present in solutions even at an significant excess of the acid. To protonate the complex, it is required at least two MSA molecules. Under conditions of an excess of the base, DEA molecules do not solvate the 1 : 1 complex. The solution separates into two phases, composed of (C₂H₅)₂(H)NH⁺ · OS(O₂)CH₃⁻ complexes and pure DEA.     

Analytical potential energy function for the electronic states 2^∏1/2 and 2^∏3/2 of O^x2 （x=＋1, -1）

The splitting of potential energy levels for ground state X^2∏g of O^x2 （x = ＋1,-1） under spin-orbit coupling （SOC） has been calculated by using the spin-orbit （SO） multi-configuration quasi-degenerate perturbation theory （SO-MCQDPT）. Their Murrell-Sorbie （M S） potential functions are gained, and then the spectroscopic constants for electronic states 2^∏1/2 and 2^∏3/2 are derived from the M S function. The vertical excitation energies for O^x2 （x = ＋1,-1） are v[O2＋1^（2∏3/2→X^2∏1/2）] =195.652cm^-1, and v[O2^-1（2^∏1/2 →X^2∏3/2）] =182.568cm^-1, respectively. All the spectroscopic data for electronic states 2^∏1/2 and 2^∏3/2 are given for the first time.     

磁畴壁在复合外场中的运动方程及其在磁弹性内耗的应用

在以速率α匀速增加的磁化场中,测量铁磁性材料的内耗时,材料中畴壁所受的力除了外加磁化场所提供的主驱动力A₀⁰+A₁⁰αt,以及测量内耗所用交变应力所提供的微扰交变驱动力A₃⁰sinωt之外,经分析表明,还存在一项在数值上与主驱动力及交变驱动力的乘积成正比的交互作用驱动力,可写为A₂⁰sinωt。这里的A₀关键词：     

Resonance Raman spectroscopy and theoretical study on the photodissociation dynamics of diuron in S2 state

Resonance Raman spectra (RRs) and quantum chemical calculations were used to investigate the photodissociation dynamics of diuron in S₂ state. The RRs indicate that the photorelaxation dynamics for the S₀ → S₂ excited state is predominantly along nine motions: the ring C = C stretch vibration ν₁₂ (1593 cm⁻¹), Ph–N–H wag ν₁₄ (1517 cm⁻¹), CO–N(CH₃)₂ stretch ν₂₃ (1365 cm⁻¹)_, CCH wag in plane/ring C = C stretch ν₂₄ (1297 cm⁻¹)_, ring CH rock in plane/ring deformation ν₂₇ (1233 cm⁻¹), CCH wag in plane ν₂₉ (1151 cm⁻¹), Ph–Cl (para) stretch ν₃₅ (1028 cm⁻¹), Ph–N–H wag ν₃₇ (913 cm⁻¹) and ring breath ν₄₄ (685 cm⁻¹). Dissociation by Ph–Cl (para) cleavage at S₂ state directly or relaxation to T₂ state by internal conversion (S₂ → S₁) and intersystem crossing (S₁/T₂) is expected by ~250 nm irradiation based on the RRS, complete active space self‐consistent field, configuration interaction singles and time‐dependent density functional theory calculations. Copyright © 2012 John Wiley & Sons, Ltd.     

无定形靶中离子注入的R,Rp,△Rp的理论计算

本文在Thomas-Fermi势能基础上,导出了全射程R的解析解:R=2/a[E^1/2-A₁(arctg(2E^1/2-f)/△^1/2+arctg f/△^1/2)+B₁ln((E^1/2-f)²)/(E-fE^1/2+d) ·d/f²],其中A₁,B₁,f,d和△均为与离子及靶的质量、原子序数有关的常数。结合导出的η=R/(R_p)(R_p指投影射程)比值的双曲线函数关系 η=F(μ)[A₂(μ)+(B₂(μ))/(ε^1/2+C)],和ω=R_p/△R_p(△R_p指投影射程的标准偏差)比值的线性关系ω=A₃(μ)ε^1/21/2+B₃(μ),可简便而又准确地计算R,△R_p,R_p.这里F(μ),A₂(μ),B₂(μ), B₃(μ)和A₃(μ)为μ的代数函数,μ为离子与靶的质量比,C是经验常数.并对η等关系式的物理意义作了讨论。上述公式的计算结果与Gibbons的数值解结果及有关实验结果作了比较,表明可用于元素半导体如Si、二元化合物如GaAs以及三元化合物如SiO₂等;既对较轻离子适用,也对重离子适用,具有一定的普适范围。     

The vertical spectrum of H2CO revisited: (SC)2-CI and CC calculations

The vertical electronic spectrum of formaldehyde has been studied by means of (SC)²-MR-SDCI and CCLR methods. Two basis sets of atomic natural orbitals (ANOs) complemented with a one-centre series of Rydberg orbitals were used. The first was taken from the CASPT2 study by Merchán, M., and Roos, B. O., 1995, Theoret. Chim. Acta, 92, 221, and may be described as C,O[4s3pld]/H[2slp] with a lslpld Rydberg series centred in the charge centroid of the ²B₂ state of the cation. The second was a larger basis set that may be described as C,O[6s5p3d2f]/H[4s3p2d] + 3s3p3d in the same centre. The (SC)² dressing may be applied efficiently to an MR-SDCI method and comparison with the dressed CAS-SDCI is satisfactory, in spite of the remarkable reduction in the CI space dimension. The consistency of the (SC)²-MR-SDCI results was tested also against the CCLR and CASPT2 results using the same basis sets and against the CCLR results using Dunning's aug- and daug-cc-pVQZ basis sets. The ³A₁(π → π *) state is correctly placed as the second excited triplet while the highly multi-configurational nature of the ¹A₁(π → π *) state is confirmed as well as its greatly mixed valence-Rydberg nature. This state is predicted as lying under the 10 eV level, on top of the (n_y → 3d) Rydberg states that are predicted in the 8.9–9.5eV region. The 5 ¹B₂(n^y → 4s) Rydberg state and the ¹B₂(σ_y → π*) also are predicted in this region. The triplet states also were calculated with the (SC)²-MR-SDCI method. The vertical ordering of the 2 ¹A₁(n_y → 3p_y) and 2 ¹B₂(n_y → 3p_z) states is discussed, as well as that of the ¹B₁(σ → π*) and the Rydberg ¹B₁(n_y → 3d_xy) states. This work shows the highly reliable values that may be reached applying the dressing method along with a large basis set. Such a procedure is made possible using an MR-SDCI selection of spaces instead of the CAS-SDCI that was used up to now in most (SC)² dressing applications.     

两个共线Kerr黑洞度规迭加的时空结构

本文利用虚坐标方法研究了两个共线Kerr黑洞迭加的时空结构;首次得到了这种情况下视界以内的时空区域,并给出了2z₀>(M₁²-a₁²)^1/2+(M₂²-a₂²)^1/2时内外无限红移面和奇点随z₀变化的情况。由此我们可以看到,对于角动量平行及反平行的两个共线的全同Kerr解来说,当z₀→(M²-a²)^1/2时,尽管它们视界以外的时空结构分别趋于一个Kerr时空及一个Schwarzschild-NUT时空,但就整个时空结构而言,并非如此。同时,我们还可看到,当2z₀>(M₁²-a₁²)^1/2+(M₂²-a₂²)^1/2时,Einstoin场方程存在无裸奇点(而不是没有奇点)的解。 关键词：