Observation of OH angular momentum polarization produced by H+O2 at 2.6 eV collision energy

The OH rotational polarization produced by the reaction of fast H atoms from the polarized 193 nm photolysis of HBr with O₂ (2.6 eV collision energy) has been measured by laser-induced fluorescence using polarized analysis light. A strong rotational polarization parallel to the electric vector of the dissociation laser and perpendicular to the flight direction of the H atoms is observed. Implications for the H+O₂ reaction dynamics at high collision energies are discussed.     

2D single-shot imaging of OH radicals using tunable excimer lasers

Three schemes for imaging OH with tunable excimer lasers are compared: Excitation and detection at 308 nm (0–0 band, XeCl laser), excitation with a KrF laser at 248 nm (3–0 band) and a new scheme using excitation at 308 nm and detection at 343 nm (0–1 band). Each scheme has certain advantages: The first scheme gives by far the highest signal, the second is less sensitive to collisional quenching and the third is suited to dirty environments because of the long excitation wavelength and off-resonance detection.     

Dye laser probing of primary C2 radicals formed by IR intense field photolysis of ethylene

The C₂-radicals in the lower electronic statea ³ II _u have been studied by the method of laser-excited luminescence of products of ethylene IR photolysis. The dependence of C₂-radical concentration on IR field power density and its time evolution have been investigated. The threshold characteristics of C₂-radical occurrence and the ratio between excited and unexcited radicals have been determined. Different mechanisms for their formation are being discussed.     

Rotational temperature measurement in high-temperature air using KrF laser-induced O2 fluorescence

Rotational temperature of O₂ has been measured in an atmospheric-air furnace using KrF laser-induced fluorescence. Average measurement errors of 10.7% and 5.1% over a temperature range of 1325–1725K were observed using two- and four-line excitation techniques, respectively. Ground-state depletion was observed for a spectral laser irradiance greater than approximately 7.5×10⁶ W/cm² cm^–1. This technique is suitable for temperature measurements when the O₂ vibrational population is not in thermal equilibrium.     

Temperature- and pressure-dependent absorption coefficients for CO2 and O2 at 193 nm

Absorption of laser radiation at 193 nm by CO₂ and O₂ was studied at a series of different temperatures up to 1273 K and pressures up to 1 bar. The spectrum for CO₂ was found to be broadband, so that absorption could be fitted to a Beer-Lambert law. On the other hand, the corresponding O₂ spectrum is strongly structured and parameterisation requires a more complex relation, depending on both temperature and the product (pressure 2 absorption path length). In this context, the influence of spectral structure on the resulting spectrally integrated absorption coefficients is discussed. Using the fitting parameters obtained, effective transmissions at 193 nm can be calculated for a wide range of experimental conditions. As an illustration of the practical application of these data, the calculation of effective transmission for a typical industrial flue gas is described.     

Rotational spectrum of HCBr produced by 193-nm laser photolysis of bromoform

The pure rotational spectrum of bromomethylene (HCBr) was studied by kinetic microwave spectroscopy between 420 and 472 GHz. The HCBr radical was produced by 193-nm ArF laser photolysis of bromoform (CHBr₃). More than 130 rotational transitions for both and species in the ground vibrational state were measured involving 1?J?33 and 0?K_a?5. The spectra were well described by an S-reduced Watson Hamiltonian in the I^r representation including the nuclear quadrupole and spin-rotation hyperfine terms. Rotational, centrifugal distortion, nuclear quadrupole and spin-rotation coupling constants were derived for both and species in the ground vibrational state.     

Efficient production of13C2F4 in the infrared laser photolysis of CHClF2

We report the isotopically selective decomposition of chlorodifluoromethane. Chlorodifluoromethane is used industrially in high volume for the production of tetrafluoroethylene and its polymers; thereby it is an attractive working substrate for a medium scale isotope separation process, both in terms of its price and availability.We have studied the infrared multiphoton decomposition of carbon-13 substituted chlorodifluoromethane molecules present at their natural abundance (1.11%). A well defined CO₂ laser pulse (80 ns FWHM) was used and both the yield of carbon-13 enriched product and the net absorption of laser radiation were measured. These measurements were made as a function of substrate pressure (10-800 Torr), CO₂ laser line (9P 12–9P 32) and fluence (2–8 J cm^–2) and were used to determine the energy expenditure per carbon atom produced () at specified product carbon-13 content in the range 30%–96%. The results of these parametric studies were interpreted in terms of the kinetics of multiphoton absorption and dissociation, and allowed an initial optimization of the experimental conditions to minimize .Optimum results were obtained at 1046.9 cm^–1, 69 cm^–1 to the red of the¹²CHClF₂ v ₉ band center. Irradiation of 100 Torr of chlorodifluoromethane at 3.5 J cm^–2 gave tetrafluoroethylene containing 50% carbon-13 for an absorption of 140 photons (0.017 keV) per carbon atom produced. This efficiency compares favourably with existing carbon-13 enrichment technologies and would require an absorption pathlength of only 2 m to absorb half the incident photons.Issued as NRCC 20112     

Quenching of fluorescence from Na(32P) and K(42P) atoms following photodissociation of NaCl and KCl at 193 nm

 Quenching of fluorescence from Na(3² P) and K(4² P) atoms by various collision partners was studied at 973 and 1273K. Excited alkali atoms were produced photolytically by excimer laser light at 193nm. For each collision pair, the appropriate relative velocity was computed and used to evaluate the quenching cross-section from the measured rate constants. Cross sections for CO₂, O₂ and N₂ are large (10–60Ų) while for Ar, the values are <1 Ų. The results are compared with those of previous investigations as a function of relative velocity. Finally, implications for combustion diagnostics are briefly discussed. Received: 29 March 1996     

The 193 nm photolysis of NO2: NO(ν) vibrational distribution,O(1D) quantum yield and emission from vibrationally excited NO2

Time resolved Fourier transform infrared emission has been used to study the photolysis of NO2 and its dimer N2O4 at 193 nm. NO(ν) populations from the photolysis of NO2 show a bimodal distribution, peaking at ν = 5 and with a subsidiary maximum at ν = 14, close to the energetically allowed limit. The results are discussed in terms of previous measurements near this photolysis wavelength of the kinetic energies of the two possible O atomic fragments, O(3P) and O(1D), and on the electronic states of the parent molecule which can be populated. The O(1D) yield has been measured as 0.51 ± 0.04, in good agreement with previously reported values. Emission from vibrationally excited NO2 arises from the dissociation of N2O4 and is similar to that observed from photolysis at 248 nm.     

H+H2O reaction dynamics: state distribution for the OH product

A method has been developed to study the dynamics of high barrier reactions by combining hot-atom production by laser photolysis and fast-product detection by laser induced fluorescence. The nascent OH rotational, vibrational and fine structure state distributions produced in the endothermic reaction have been measured with hot hydrogen atoms from the photodissociation of HBr at 193 nm. OH rotational excitation is low and corresponds to a partitioning of only around 3% of the total reaction energy to OH rotation. OH could only be observed in the vibrational ground state, i.e.(v=1)/(v=0)0.1. The OH spin doublets are produced statistically, but the partitioning in the -doublets is very non-statistical with a strong preference for the ⁺-component ((⁺)/(^–)=3.2±1.0) demonstrating the exit channel of the reaction to be preferentially planar. By measuring reactant and product densities at short times, an absolute total cross-section of 0.24±0.1[Ų] has been obtained.     

Scavenging of OH(*) radicals produced from H(2)O sonolysis with nitrate ions

The scavenging of OH(?) radicals formed during H(2)O sonolysis with nitrate-ions was studied in HNO(3)/NaNO(3) mixture at the constant NO(3)(-) ions concentration ([HNO(3)]+[NaNO(3)])=1 M in Ar atmosphere. Small amounts of N(2)H(5)NO(3) was added to solutions to avoid HNO(2) accumulation due to HNO(3) sonolysis. It was shown that the increase of [H(+)] causes the increase of H(2)O(2) formation rate (W(H(2)O(2)). (W(H(2)O(2)) values reach the plateau at [HNO(3)] approximately 1 M. The (W(H(2)O(2)) ratio in solution with [H(+)]=1 M and pure water was found to be equal to 2.4+/-0.4. It was assumed that (W(H(2)O(2)) increase in nitric acid medium is related to the changing of H(2)O(2) formation mechanism. In pure water H(2)O(2) is formed due to the OH(*) radicals recombination. In HNO(3)+NaNO(3) mixture the mechanism of H(2)O(2) formation consists in conversion of OH(*) radicals to NO(3)(*) radicals followed by NO(3)(*) radicals hydrolysis. Results obtained show that OH(*) radicals recombination mainly occurs in the liquid phase surrounding the cavitating bubble.     

Pulsed-laser photolysis of Mn2(CO)10: A time-resolved fluorescence study

Mn₂(CO)₁₀ was photolysed in the gas phase by the XeCl-excimer laser with fluence in the range 25–300 mJ/cm² and a dye laser. The UV/VIS emission of the products was probed on a nanosecond time scale. The emission from excited states of metal atoms was detected only. The Mn atoms are predominantly formed in their ground statea ⁶ S _{2 1/2}. The absorption of one photon and the subsequent relaxation process leads to the formation ofz ⁶ P _J ⁰ (J = 11/2, 21/2, 31/2) states and emission of photons at a wavelength of 403 nm. The formation of the excited statese ⁸ D _{5 1/2},z ⁶ F _{4 1/2} ⁰ ande ⁶ D _{4 1/2} and the subsequent emission observed at wavelengths of 357, 383 and 446 nm requires the absorption of two photons by the ground-state Mn atoms. In addition, transition from thea ⁶ D _j (J = 11/2, 21/2) lower states were observed in the wavelength-resolved Laser-Induced Fluorescence (LIF) spectra.     

Experimental study of laser-induced thermal ignition in O2/O3 mixtures

O₂/O₃ mixtures are ignited by absorption of laser pulses of a TEA CO₂ laser along the axis of a cylindrical cell. The dependence of the radial propagation of the O₃ decomposition, detected by uv absorption of the ozone, on laser fluence and on O₃ concentration is investigated. Oscillations of the signals are identified to be the first radial acoustic mode of the cell. For mixtures of 0.35 bar and 0.70 bar total pressure and O₃ percentages within 20–50%, the ignition limit is in the order of 0.1–0.2 J/cm³ (absorbed energy density). These values are in reasonable agreement with the results of the corresponding numerical simulations.     

UV laser photochemistry of acetylene at 193 nm

ArF laser photolysis of acetylene at 193 nm yields diacetylene, ethylene and hydrogen (besides a polymer). No benzene or vinylacetylene is formed. Photolysis with deuterium gives no deuterated compounds. These observations are taken as evidence for a pure excited-molecule mechanism based upon C₂H ₂ ^* (¹ A _u).     

时间切片离子速度成像技术关于MgO在193 nm的光解反应动力学研究

本文利用时间切片离子速度成像技术对MgO分子在193 nm下的光解反应动力学进行了研究. 实验通过产物Mg的速度和角度分布分析,发现了三个光解反应路径. 路径一为MgO(X¹Σ⁺)态分子吸收一个光子到MgO(G¹π) 态,由于G¹π, 3³π和1⁵π态之间的自旋轨道耦合作用,反应沿着1⁵π的势能面解离生成产物Mg(³P_u)+O(³P_g). 路径二、三分别为MgO(A¹π)态分子吸收一个光子到MgO(G¹π)态和MgO(4¹π) 态,进而解离生成产物Mg(³P_u)+O(³P_g)和Mg(¹S_g)+O(¹S_g). 光解离路径的各向异性参数与振动能级的寿命以及转动和振动自旋轨道态的耦合有关. 从总动能分析得到D₀(Mg-O)=21645±50 cm^-1.     

Rotational excitation of H2O by cold electrons

Experimental data are presented for the scattering of electrons by H2O between 17 and 250 meV impact energy. These results are used in conjunction with a generally applicable method, based on a quantum defect theory approach to electron-polar molecule collisions, to derive the first set of data for state-to-state rotationally inelastic scattering cross sections based on experimental values.     

Laser-assisted etching of gallium arsenide in chlorine at 308 nm

Xenon chloride (308 nm) excimer laser-assisted etching of GaAs (100) in Cl₂ was demonstrated and characterized with respect to laser and gas parameters. The etch rate increased linearly with laser fluence from thresholds in the range of 50 to 75 mJ/cm² to the highest fluence studied, 650 mJ/cm². For a laser fluence of 370 mJ/cm², the etch rate varied with Cl₂ pressure reaching a maximum at a Cl₂ pressure of about 2 Torr. The etch rate decreased monotonically with Ar buffer gas pressure because of redeposition of GaCl₃ products into the etched channel. The redeposited GaCl₃ affected the etch rate and the etch morphology. The etch rate and morphology also varied with laser repetition rate. The mobility of chlorine on the surface also plays an important role in the etching mechanism.     

Isotope selective laser enhancement of the Li+H2 reaction

The enhancement of the Li+H₂LiH+H reaction due to laser excitation of the Li atom to the2p state has been investigated using absorption techniques. Using a rate equation model we obtain from our data a reaction cross-section [Li(2p)+H₂LiH+H]=(0.10±0.03)Ų at 515°C. By selectively exciting one Li isotope the reaction is made isotope selective, suggesting an efficient means of isotope separation.     

Enhanced birefingence of MgF2 thin film at 193 nm by serial bideposition

Magnesium fluoride films were coated by serial bideposition with a varying number of sub-deposited layers. The deposition angle 70° remained constant throughout the process by a single electron-beam source. One, 4, 20, and 100 sub-deposition layers were prepared. The microstructure, residual stress, absorption of water, and linear birefringence of serial bideposition of anisotropic thin film at 193 nm were investigated and discussed. Microstructures of the films were observed by scanning electron microscopy. The residual stress was measured by phase-shifting interferometer. The water absorption bands of the thin films were measured by Fourier transform infrared (FTIR) spectroscopy, and refractive indices in two different directions (S- and P-polarized) were determined from a spectrometer equipped with a polarizer. The linear birefringence would increase and the stress would decrease when the sub-deposited layers were increased. When the number of layers was 100, the difference between the refractive indices for two different polarizations was able to reach 0.082.     

退火对电子束热蒸发193nm Al2O3/MgF2反射膜性能的影响

设计并镀制了193nm Al2O3/MgF2反射膜,对它们在空气中分别进行了250-400℃的高温退火,测量了样品的透射率光谱曲线和绝对反射率光谱曲线.发现样品在高反射区的总的光学损耗随退火温度的升高而下降,而后趋于饱和.采用总积分散射的方法对样品在不同退火温度下的散射损耗进行了分析,发现随着退火温度的升高散射损耗有所增加.因此,总的光学损耗的下降是由于吸收损耗而不是散射损耗起主导作用.对Al2O3材料的单层膜进行了同等条件的退火处理,由它们光学性能的变化推导出它们的折射率和消光系数的变化,从而解释了相应的多层膜光学性能变化的原因.反射膜的反射率在优化联系、镀膜工艺与退火工艺的基础上达98%以上.