Experimental study on the system of Cl/Cl_2/He/HN_3/I_2

Using a microwave generator, chlorine diluted by helium was dissociated to chlorine atoms that subsequently reacted with hydrogen azide to produce the excited states of NCl(a1△). Meanwhile, molecular iodine with carrier gas of helium reacted with atomic chlorine to produce atomic iodine which then was pumped to excited state of I(2P1/2) by an energy transfer reaction from NCl(a1△). In this paper, the changes of NCl(a1△) and NCl(b1∑) emission intensity is presented when I2/He is introduced into the stream of Cl/Cl2/He/HN3/NCl(a1△)/NCl(b1∑). The dependences of atomic iodine I(2P1/2) on flow rates of gases were also investigated. The optimum parameters for I(2P1/2) production are given.     

The He/Cl2 laser at 258 nm

Lasing from e-beam pumped He/Cl₂ mixtures at 258 nm was investigated in a longitudinal pumping geometry. Time dependence, output powers and energies as well as the spectral composition of the laser pulses were determined for different experimental conditions. Optical gain was observed for eight transitions around 258 nm. The fine structure results from isotopic splitting and contributions from different vibrational states. No bottle-necking occurs. However, saturation and absorption by excited states limited the total output power to 6MW and the output energies to 200 mJ. A simple kinetic model is proposed that reproduces the larger number of experimental data quite sufficiently.     

Optical characteristics of the plasma of a transverse volume discharge in Cl2 and He/Cl2 mixtures

Results are presented from a study of UV and VUV emission from the plasma of a transverse volume discharge in chlorine and a He/Cl₂ mixture. In the wavelength range Δλ=140–300 nm, the Cl₂(D′-A′) band with an edge at 258 nm and the Cl ₂ ^* band with edge at λ=195 nm are found to be dominant. It is shown that, in the pressure range [Cl₂]=0.1–2.0 kPa, the intensity of emission with λ≤195 nm is higher than the intensity of the Cl₂(D′-A′) band. At [Cl₂]≥2 kPa, emission in the 258-nm band is dominant.     

Cl/HN3/I2全气相化学激光体系的化学动力学模拟计算

 对Cl/HN₃/I₂产生NCl(a)/I激光的过程进行了化学动力学计算，主要考察了Cl,HN₃和I₂的初始粒子数密度及其配比对小信号增益系数的影响。结果发现,当温度为400K, 初始Cl粒子数密度为1×10¹⁵，1×10¹⁶和1×10¹⁷cm^-3时,小信号增益系数分别达到1.6×10^-4,1.1×10^-3和1.1×10^-2cm^-1，获得最佳小信号增益系数的HN₃和I₂的初始粒子数密度分别为初始Cl粒子数密度的1～2倍和2%～4%。同时，对Cl，HN₃和I₂配比对小信号增益系数和增益持续时间的影响进行了讨论。     

13C-selective IRMPD of CBr2F2/Cl2 and CCl2F2/Br2 systems

The CO₂ TEA laser irradiation of CBr₂F₂ in the presence of Cl₂ yielded ¹³C-enriched CBrClF₂ and ¹³C-enriched CCl₂F₂ under selected experimental conditions. As the photolysis proceeded, the ¹³C concentration of CBrClF₂ decreased gradually and that of CCl₂F₂ increased up to 90% or higher. These results can be explained by the mechanism involving the secondary ¹³C-selective IRMPD of the primary product CBrClF₂. On the other hand, the carbon-containing product for a CCl₂F₂/Br₂ system was only CBrClF₂; the further IRMPD of which probably regenerated CBrClF₂ in the presence of Br₂. The decomposition probabilities of ¹²C- and ¹³C-containing molecules in both systems were measured as functions of laser line, laser fluence, and reactant pressures.     

Infrared intensity analysis of CH2Cl2 and CD2Cl2 in vapour and liquid states

In the infrared spectra of molecules with more than one C-H bond the symmetric and antisymmetric stretching bonds often overlap, causing uncertainty in the intensity analysis. For CH₂Cl₂ and CD₂Cl₂ in the vapour state, the two bands overlap to such an extent that Straley who takes it as one band attributes it to antisymmetric stretching while Saekiet al assign it to the symmetric stretching. Following the method of analysis initiated in this laboratory, we have solved this problem by ultimately obtaining intensities separately forA ₁ andB ₂ species. The band is mostly due to the symmetric stretching, 0.06 out of the total of 0.31 contributing toB ₂. Thus, this gives a method of separating the intensities of bands which are highly overlapping. Presented at the Symposium on Crystallography and Crystal Physics, Osmania University, Hyderabad held on 5–7, December 1977.     

Transmission of 3471 a laser radiation through Cl2 and Cl2-inert-gas mixtures

Experimental results are presented on transmission and pulse-delays of the output from a frequency- doubled ruby laser through Cl₂ and Cl₂-inert-gas mixtures. The experimental findings are consistent with the idea that the observed results are determined by competition between a not-understood quantum-mechanical coherence effect and dephasing collisions. On this assumption, we deduce reasonable estimates for applicable cross sections in collisions of Cl₂ with Cl₂, He or Ar. Since the upper state of the absorbing molecule is unstable in times of the order of 10^-12 sec, the McCall-Hahn theory for self-induced transparency is not applicable to our system.     

Relative Cl 2p:P 2s photoionization intensities in transition metal complexes

X-ray photoelectron spectra of the Cl 2p_{$\text{1}\text{2}$, $\text{3}\text{2}$}, P 2s region were obtained for nine transition metal complexes. The Cl:P atom ratios ranged from 1:3 to 3:2 and exhibited a linear relationship with the Cl 2p_{$\text{1}\text{2}$, $\text{3}\text{2}$} : P 2s intensities. Using AlKα radiation, the ratio of the Cl 2p: P 2s photoionization intensities was found to be 2.5: 1.0 with the McPherson ESCA-36 Photoelectron Spectrometer operated in its standard configuration.     

Surface analysis of Hg2Cl2

A surface composition of (110) face of Hg₂Cl₂ in high vacuum is studied for the room temperature. The impact of primary electrons with energy of 2·5 keV causes a decomposition of the surface layer which is described in detail.The single crystals of Hg₂Cl₂ used in this work were prepared by Dr. Barta in Institute of Solid State Physics of Czechosl. Acad. Sci., Prague.     

全谱火焰光度法检测硫、磷、氮、砷、氯元素

火焰光度分析技术是一种能够快速灵敏检测硫、磷等元素的成熟方法。在环境检测,农残检测,工农业生产领域得到广泛应用。通过对传统火焰光度检测器的改进设计,采用光栅和CCD传感器阵列作为检测器的光电转换器件,拓展了检测化合物的种类,成功实现了对H2S,PH3,NH3,AsH3,Cl2为代表的硫、磷、氮、砷、氯五种元素的实时检测。由原来依靠特征波长检测拓展到利用物质火焰光度光谱信息进行定性定量分析。结合化学计量学的方法有望成为一种能够同时检测多类有毒有害气体的快速现场检测技术。     

35Cl nuclear quadrupole resonance and the macroscopic superstructure in Hg2Cl2 crystal

A study has been made of the temperature dependences of the chlorine NQR frequency and linewidth in calomel crystals. These dependences show clearly pronounced anomalies in the region of the ferroelastic phase transition. The dynamic and static factors influencing the pattern of these dependences are discussed. A fine structure in the spin echo in the form of beats has been revealed within a narrow temperature interval near the phase transition. This effect is shown to be connected with the formation of a macroscopic heterophase superstructure in the crystal. Fiz. Tverd. Tela (St. Petersburg) 39, 1287–1290 (July 1997)     

CH2Cl和O2的反应动力学

利用时间分辨傅立叶变换红外发射光谱技术研究了CH2Cl+O2的气相基元反应．在实验中首次观测到了振动激发产物CO (v·4)和CO2(o3,v·7)．激发态的CO/CO2 (o3)比率是72.2§7．在QCISD//UB3LYP/6-311++G (d, p)水平上对该化学反应的中间物和产物进行了量子化学计算．其研究结果表明: CH2Cl 自由基首先和O2结合, 生成中间物CH2ClOO， 紧接着发生脱氯反应生成环氧中间物CH2OO，然后再经过一系列的异构化和分解反应，生成最终的产物CO和CO2，和实验观     

Dissociative electron attachment to CF2Cl2

Using a recently constructed high resolution crossed electron/molecular beam apparatus consisting of a hemispherical electron monochromator and a quadrupole mass spectrometer we have measured the relative production cross sections for CI^– and F^– via electron attachment to CF₂Cl₂. The relative Cl^– cross section is placed on an absolute scale by reference to an absolute rate coefficient using a calibration method involving integration of the measured anion signal. The most efficient Cl^– production process is at about zero energy and its magnitude is resolution limited. The present high resolution value of 6 × 10^–16 cm² compares well with an earlier value reported by Chen and Chantry. A second peak is detected at around 0.8 eV in accordance with some of the earlier beam and swarm measurements. The observed production of F^– has an appearance energy of 1.9 eV and the energy of maximum cross section is 3.36 eV, the latter value comparing well with several previous studies.     

Electron density in Si2 and Cl2

Self consistent field-Xα molecular orbital calculations have been performed for Si₂ and Cl₂ using both the scattered-wave (SW) and LCAO discrete-variational (DV) versions of the method. For Si₂ an SW calculation including f partial waves yields orbital densities in good agreement with those from methods which do not involve the muffin-tin approximation for the potential. The present results afford a further comparison relevant to the recent discussion (see, M. Schlüter et al. [9]) of the relative accuracy of various pseudocharge densities compared with real charge densities. The deformation density from the Xα-SW calculation is in good agreement with that from the DV-Xα method and also with that from the linear muffin tin orbital method (J. Harris and R. O. Jones [8]). Differences between the valence electron distribution which is usually discussed in connection with pseudopotential schemes, and the density distribution including the 2s and 2p core electrons are delineated. For Cl₂, the Xα-SW deformation density shows positive lobes along lines through the atoms perpendicular to the bond axis, is negative for most of the area between the atoms and also shows negative lobes behind the atoms. This deformation map is in good qualitative agreement with the DV-Xα map and also with recent ab initio results with the exception of a small region at the centre of the bond in which the DV-Xα and ab initio results show an excess of electrons compared with the promolecule whereas the Xα-SW results show a deficiency. Comparisons with X-ray results on solid chlorine are inconclusive so that experimental electron scattering data on gas phase chlorine will be required to resolve this difference.     

Phase Behavior of Liquid Crystals Formed in [C12mim]Cl/H2O and [C12mim]Cl/Alcohols Systems

利用偏光显微镜及小角X射线散射研究了25 °C下由1-十二烷基-3-甲基咪唑氯化物[C₁₂mim]Cl和水、[C₁₂mim]Cl和不同的醇(正丁醇、正戊醇、正己醇、正辛醇)所形成的二元体系的相行为. 结果表明：[C₁₂mim]Cl和水可以形成六角相,其晶格参数随[C₁₂mim]Cl含量的增多而递减;[C₁₂mim]Cl和不同的醇可以形成层状相,且醇的碳链越长,层状相越易形成. 与水做溶剂相比,在[C₁₂mim]Cl/辛醇体系中,随[C₁₂mim]Cl含量的增加,层状相的层间距反而增大. 通过变温小角X射线散射和差示扫描量热法研究表明：层状相在高于室温的较大温度范围内是稳定的. 由于温度升高使[C₁₂mim]Cl的碳氢链变软并易于缠结,导致层间距随温度的升高而减小. 通过红外光谱可以证明包含咪唑头基、氯离子和辛醇的氢键网络的存在. 疏溶剂力和氢键网络的协同作用是[C₁₂mim]Cl能形成六角相和层状相的关键.     

Isomeric Cl(2)O(2)(+) and Cl(2)O(2)(-) ions

Charged species structurally related to several isomers of Cl(2)O(2), of considerable importance in atmospheric chemistry, were obtained by chemical ionization (CI) and characterized by collisionally activated dissociation (CAD) mass spectrometry. The ClOClO(+) and [Cl(2)-O(2)](+) species were prepared by positive ion Cl(2)/CI of ClO(2) and O(2), respectively, whereas the ClClO(2)(+) isomer proved an elusive species of considerably lower stability. The ClClO(2)(-) anion was obtained from the negative ion Cl(2)/CI of ClO(2). The formation process, structure and stability of the ions are discussed in connection with available theoretical results and related to the recent preparation of (Cl(2)O(2))(+)SbF(6)(-) and (Cl(2)O(2))(+)Sb(2)F(11)(-) salts in the solid phase. Copyright 1999 John Wiley & Sons, Ltd.     

Neutron scattering study of the two-dimensional spinS=1/2 square-lattice Heisenberg antiferromagnet Sr2CuO2Cl2

We have carried out a neutron scattering investigation of the static structure factorS(q _2D ) (q _2D is the in-plane wave vector) in the two-dimensional spinS=1/2 square-lattice Heisenberg antiferromagnet Sr₂CuO₂Cl₂. For the spin correlation length we find quantitative agreement with Monte Carlo results over a wide range of temperature. The combined Sr₂CuO₂Cl₂-Monte Carlo data, which cover the length scale from 1 to 200 lattice constants, are predicted without adjustable parameteres by renormalized classical theory for the quantum nonlinear sigma model. For the structure factor peakS(0), on the other hand, we findS(0) ² for the reduced temperature range 0.16<T/2 _s <0.36, whereas current theories predict that at low temperaturesS(0)T ^{2 2}. This discrepancy has important implications for the interpretation of many derivative quantities such as NMR relaxation rates. In the ordered phase, we have measured the temperature dependence of the out-of-plane spin-wave gap. Its low-temperature value of 5.0 meV corresponds to an XY anisotropyJ _XY /J=1.4×10^–4. From measurements of the sublattice mangetization we obtain =0.22±0.01 for the order parameter exponent. This may either reflect tricricality as in La₂CuO₄, or it may indicate finite-size two-dimensional XY behavior as suggested by Bramwell and Holdsworth. As in theS=1 system K₂NiF₄, the gap energy in Sr₂CuO₂Cl₂ scales linearly with the order parameter up to the Néel temperature. We also reanalyze static structure factor data for K₂NiF₄ using the exact low temperature result for the correlation length of Hasenfratz and Niedermayer and including the Ising anisotropy explicitly. Excellent agreement between experiment and theory is obtained for the correlation length, albeit with the spin-stiffness _s reduced by 20% from the spin-wave value. As in Sr₂CuO₂Cl₂ we find thatS(0) ² for the reduced temperature range 0.22<T/2 _s <0.47.     

CO2-laser-induced multiphoton absorption of CF2Cl2

Energy absorption by CF₂Cl₂ from an intense TEA CO₂ laser pulse is measured as a function of the pressure of CF₂Cl₂ and the pressure of Ar bath gas for different laser energy fluences. The fraction of the molecules excited by the laser field and the average energy of the molecular ensemble are determined by a simple experimental method.