在激波波面中氧分子的非平衡离解

对强激波作用下双原子分子振动与离解耦合的非平衡离解过程进行了理论计算.本工作的特点是将计算起点建立在分子基本参数上,采用主方程理论处理振动与离解的耦合,振动跃迁几率用SSH理论计算,在离解限附近考虑多量子数跃迁并计及原子复合的影响.对O2-Ar体系,计算给出了在正激波后O2分子振动能级分布、振动弛豫时间、离解孕育时间、离解产物浓度、离解速率系数等物理量随时间的演化.计算结果分别与Camac和Wray的实验相符.计算显示,在激波作用的后期,有准稳态的振动能级布居分布.计算结果显示,Park模型低估了非平衡离解速率系数,Hansen模型则高估了非平衡离解速率系数.

Computation of turbulence-generated noise by large-eddy simulation

The hybrid method of large eddy simulation (LES) and the Lighthill analogy is being developed to compute the sound radiated from turbulent flows. The results obtained from the hybrid method are often contaminated by the absence of small scales in LES, since the energy level of sound is much smaller than that of turbulent flows. Previous researches investigate the effects of subgrid sacle (SGS) eddies on the frequency spectra of sound radiated by isotropic turbulence and suggest a SGS noise model to represent the SGS contributions to the frequency spectra. Their investigations are conducted in physical space and are unavoidably influenced by boundary conditions. In this paper, we propose to perform such calculations in Fourier space so that the effects of boundary conditions can be correctly treated. Posteriori tests are carried out to investigate the SGS contribution to the sound. The results obtained recover the -7/2 law within certain wave-number ranges, but under-estimate the amplitudes of the frequency spectra. The reason for the underestimation is also discussed.

Geochemistry and resonance ionization of platinum-group elements

Experimental studies were conducted with the goals of 1) determining the origin of Pt- group element (PGE) alloys and associated mineral assemblages in refractory inclusions from meteorites and 2) developing a new ultrasensitive method for the in situ chemical and isotopic analysis of PGE. A general review of the geochemistry and cosmochemistry of the PGE is given, and specific research contributions are presented within the context of this broad framework.

An important step toward understanding the cosmochemistry of the PGE is the determination of the origin of POE-rich metallic phases (most commonly εRu-Fe) that are found in Ca, AJ-rich refractory inclusions (CAI) in C3V meteorites. These metals occur along with γNi-Fe metals, Ni-Fe sulfides and Fe oxides in multiphase opaque assemblages. Laboratory experiments were used to show that the mineral assemblages and textures observed in opaque assemblages could be produced by sulfidation and oxidation of once homogeneous Ni-Fe-PGE metals. Phase equilibria, partitioning and diffusion kinetics were studied in the Ni-Fe-Ru system in order to quantify the conditions of opaque assemblage formation. Phase boundaries and tie lines in the Ni-Fe-Ru system were determined at 1273, 1073 and 873K using an experimental technique that allowed the investigation of a large portion of the Ni-Fe-Ru system with a single experiment at each temperature by establishing a concentration gradient within which local equilibrium between coexisting phases was maintained. A wide miscibility gap was found to be present at each temperature, separating a hexagonal close-packed εRu-Fe phase from a face-centered cubic γNi-Fe phase. Phase equilibria determined here for the Ni-Fe-Ru system, and phase equilibria from the literature for the Ni-Fe-S and Ni-Fe-O systems, were compared with analyses of minerals from opaque assemblages to estimate the temperature and chemical conditions of opaque assemblage formation. It was determined that opaque assemblages equilibrated at a temperature of ~770K, a sulfur fugacity 10 times higher than an equilibrium solar gas, and an oxygen fugacity 10⁶ times higher than an equilibrium solar gas.

Diffusion rates between -γNi-Fe and εRu-Fe metal play a critical role in determining the time (with respect to CAI petrogenesis) and duration of the opaque assemblage equilibration process. The diffusion coefficient for Ru in Ni (D^Ru_Ni) was determined as an analog for the Ni-Fe-Ru system by the thin-film diffusion method in the temperature range of 1073 to 1673K and is given by the expression:

D^Ru_Ni (cm² sec^-1) = 5.0(±0.7) x 10^-3 exp(-2.3(±0.1) x 10¹² erg mole^-1/RT) where R is the gas constant and T is the temperature in K. Based on the rates of dissolution and exsolution of metallic phases in the Ni-Fe-Ru system it is suggested that opaque assemblages equilibrated after the melting and crystallization of host CAI during a metamorphic event of ≥ 10³ years duration. It is inferred that opaque assemblages originated as immiscible metallic liquid droplets in the CAI silicate liquid. The bulk compositions of PGE in these precursor alloys reflects an early stage of condensation from the solar nebula and the partitioning of V between the precursor alloys and CAI silicate liquid reflects the reducing nebular conditions under which CAI were melted. The individual mineral phases now observed in opaque assemblages do not preserve an independent history prior to CAI melting and crystallization, but instead provide important information on the post-accretionary history of C3V meteorites and allow the quantification of the temperature, sulfur fugacity and oxygen fugacity of cooling planetary environments. This contrasts with previous models that called upon the formation of opaque assemblages by aggregation of phases that formed independently under highly variable conditions in the solar nebula prior to the crystallization of CAI.

Analytical studies were carried out on PGE-rich phases from meteorites and the products of synthetic experiments using traditional electron microprobe x-ray analytical techniques. The concentrations of PGE in common minerals from meteorites and terrestrial rocks are far below the ~100 ppm detection limit of the electron microprobe. This has limited the scope of analytical studies to the very few cases where PGE are unusually enriched. To study the distribution of PGE in common minerals will require an in situ analytical technique with much lower detection limits than any methods currently in use. To overcome this limitation, resonance ionization of sputtered atoms was investigated for use as an ultrasensitive in situ analytical technique for the analysis of PGE. The mass spectrometric analysis of Os and Re was investigated using a pulsed primary Ar⁺ ion beam to provide sputtered atoms for resonance ionization mass spectrometry. An ionization scheme for Os that utilizes three resonant energy levels (including an autoionizing energy level) was investigated and found to have superior sensitivity and selectivity compared to nonresonant and one and two energy level resonant ionization schemes. An elemental selectivity for Os over Re of ≥ 10³ was demonstrated. It was found that detuning the ionizing laser from the autoionizing energy level to an arbitrary region in the ionization continuum resulted in a five-fold decrease in signal intensity and a ten-fold decrease in elemental selectivity. Osmium concentrations in synthetic metals and iron meteorites were measured to demonstrate the analytical capabilities of the technique. A linear correlation between Os⁺ signal intensity and the known Os concentration was observed over a range of nearly 10⁴ in Os concentration with an accuracy of ~ ±10%, a millimum detection limit of 7 parts per billion atomic, and a useful yield of 1%. Resonance ionization of sputtered atoms samples the dominant neutral-fraction of sputtered atoms and utilizes multiphoton resonance ionization to achieve high sensitivity and to eliminate atomic and molecular interferences. Matrix effects should be small compared to secondary ion mass spectrometry because ionization occurs in the gas phase and is largely independent of the physical properties of the matrix material. Resonance ionization of sputtered atoms can be applied to in situ chemical analysis of most high ionization potential elements (including all of the PGE) in a wide range of natural and synthetic materials. The high useful yield and elemental selectivity of this method should eventually allow the in situ measurement of Os isotope ratios in some natural samples and in sample extracts enriched in PGE by fire assay fusion.

Phase equilibria and diffusion experiments have provided the basis for a reinterpretation of the origin of opaque assemblages in CAI and have yielded quantitative information on conditions in the primitive solar nebula and cooling planetary environments. Development of the method of resonance ionization of sputtered atoms for the analysis of Os has shown that this technique has wide applications in geochemistry and will for the first time allow in situ studies of the distribution of PGE at the low concentration levels at which they occur in common minerals.

LiNbO3：Fe：Ni晶体非挥发全息存储研究

采用三种不同的双光记录方案进行了LiNbO3：Fe：Ni晶体全息存储实验．详细研究了饱和衍射效率、固定衍射效率、动态范围和记录灵敏度，以及退火条件对记录的影响。结果表明，氧化LiNbO3：Fe：Ni晶体的饱和衍射效率、固定衍射效率和记录灵敏度比其他报道的双掺杂LiNbO3晶体高。结合掺杂能级图，理论分析了LiNbO3双掺杂晶体深陷阱中心能级的相对位置及其微观光学参量对全息记录性能的影响。LiNbO3：Fe：Ni晶体有望成为一种新的高效率非挥发全息存储材料。

Nature of the radical intermediates in a substituted cyclopropylcarbiny-allylcarbinyl system

We have sought to determine the nature of the free-radical precursors to ring-opened hydrocarbon 5 and ring-closed hydrocarbon 6. Reasonable alternative formulations involve the postulation of hydrogen abstraction (a) by a pair of rapidly equilibrating classical radicals (the ring-opened allylcarbinyl-type radical 3 and the ring-closed cyclopropylcarbinyl-type 4), or (b) by a nonclassical radical such as homoallylic radical 7.

[Figure not reproduced.]

Entry to the radical system is gained via degassed thermal decomposition of peresters having the ring-opened and the ring-closed structures. The ratio of 6:5 is essentially independent of the hydrogen donor concentration for decomposition of the former at 125° in the presence of triethyltin hydrdride. A deuterium labeling study showed that the α and β methylene groups in 3 (or the equivalent) are rapidly interchanged under these conditions.

Existence of two (or more) product-forming intermediates is indicated (a) by dependence of the ratio 6:5 on the tin hydride concentration for decomposition of the ring-closed perester at 10 and 35°, and (b) by formation of cage products having largely or wholly the structure (ring-opened or ring-closed) of the starting perester.

Relative rates of hydrogen abstraction by 3 could be inferred by comparison of ratios of rate constants for hydrogen abstraction and ortho-ring cyclization:

[Figure not reproduced.]

At 100° values of k_a/k_r are 0.14 for hydrogen abstraction from 1,4-cyclohexadiene and 7 for abstraction from triethyltin hydride. The ratio 6:5 at the same temperature is ~0.0035 for hydrogen abstraction from 1,4-cyclohexadiene, ~0.078 for abstraction from the tin hydride, and ≥ 5 for abstraction from cyclohexadienyl radicals. These data indicate that abstraction of hydrogen from triethyltin hydride is more rapid than from 1,4-cyclohexadiene by a factor of ~1000 for 4, but only ~50 for 3.

Measurements of product ratios at several temperatures allowed the construction of an approximate energy-level scheme. A major inference is that isomerization of 3 to 4 is exothermic by 8 ± 3 kcal/mole, in good agreement with expectations based on bond dissociation energies. Absolute rate-constant estimates are also given.

The results are nicely compatible with a classical-radical mechanism, but attempted interpretation in terms of a nonclassical radical precursor of product ratios formed even from equilibrated radical intermediates leads, it is argued, to serious difficulties.

The roles played by hydrogen abstraction from 1,4,-cyclohexadiene and from the derived cyclohexadienyl radicals were probed by fitting observed ratios of 6:5 and 5:10 in the sense of least-squares to expressions derived for a complex mechanistic scheme. Some 30 to 40 measurements on each product ratio, obtained under a variety of experimental conditions, could be fit with an average deviation of ~6%. Significant systematic deviations were found, but these could largely be redressed by assuming (a) that the rate constant for reaction of 4 with cyclohexadienyl radical is inversely proportional to the viscosity of the medium (i.e., is diffusion-controlled), and (b) that k_a/k_r for hydrogen abstraction from 1,4-cyclohexadiene depends slightly on the composition of the medium. An average deviation of 4.4% was thereby attained.

Degassed thermal decomposition of the ring-opened perester in the presence of the triethyltin hydride occurs primarily by attack on perester of triethyltin radicals, presumably at the –O-O- bond, even at 0.01 M tin hydride at 100 and 125°. Tin ester and tin ether are apparently formed in closely similar amounts under these conditions, but the tin ester predominates at room temperature in the companion air-induced decomposition, indicating that attack on perester to give the tin ether requires an activation energy approximately 5 kcal/mole in excess of that for the formation of tin ester.

Yb：Y2O3透明陶瓷的光学性能研究

介绍了一种基于纳米粉末真空烧结技术的新型固体激光材料——Yb：Y2O3多晶陶瓷的制备工艺、物理化学特性、能级结构和光谱特性，并与Yb：YAG单晶进行了对比．采用紧凑型有源镜激光器（CAMIL）的抽运方式，验证了Yb：Y2O3透明陶瓷的激光输出性能．在35W的最大抽运功率下，得到波长1078nm，功率10．5w的连续激光输出，斜率效率达到37．5％．实验中还观察到激光输出波长随抽运功率增加而红移以及随输出耦合镜变化而漂移的现象．Yb：Y2O3多晶陶瓷是一种理想的激光材料，不仅具有与Yb：YAG单晶同样优秀的

Stability against crystallization and spectroscopic properties of Tm3+ doped fluorophosphate glasses

Fluorophosphate glasses with various content of Al(PO3)(3) were prepared. With the increment of Al(PO3)(3) content, density decreases while refractive index increases, and transition temperature, crystallization peak temperature and melt temperature increase which were suggested by differential scanning calorimetry. These glasses exhibit the best stability against crystallization with 7-9 mol'Yo Al(PO3)(3) content. Normalized Raman spectra were used to analyze structure and phonon state. The increment of Al(PO3)(3) content does not affect phonon energy but results in the augment of phonon density. Absorption spectra were measured. H-3(6) -> F-3(4) transition exhibits absorption at L band of the third communication window. Compared with the energy of Tm3+ excited states in other glass system, F-3(4) energy of Tm3+ in these glasses is considerable higher and H-3(4) energy is considerable lower, and it can be predicted that emission band of H-3(4) -> F-3(4) transition is close to the amplified band of gain-shift Tm3+ doped fiber amplifier. Analyses of Judd-Ofelt theory suggest when Al(PO3)(3) content is no more than 7 mol%, Judd-Ofelt parameters Omega(t) and the lifetime of H-3(4) energy level of TM3+ vary little with the increment of Al(PO3)(3) content, and when Al(PO3)(3) content is more than 7 mol%, Omega(2) and Omega(6) increase and radiative lifetime of H-3(4) energy level of Tm3+ drops sharply with the increment of Al(PO3)(3) content. (c) 2006 Elsevier B.V. All rights reserved.

Broadband near-infrared emission in Er3+-Tm3+ codoped chalcohalide glasses

The near-IR emission spectra of Er3+-Tm3+ codoped 70GeS(2)-20In(2)S(3)-10CsI chalcohalide glasses were studied with an 808 nm laser as an excitation source. A broad emission extending from 1.35 to 1.7 mu m with a FWHM of similar to 160 nm was recorded in a 0.1 mol.% Er2S3, 0.5 mol.% Tm2S3 codoped chalcohalide glass. The fluorescence decay curves of glasses were measured by monitoring the emissions of Tm3+ at 1460 nm and Er3+ at 1540 nm, and the lifetimes were obtained from the first-order exponential fit. The luminescence mechanism and the possible energy-transfer processes are discussed with respect to the energy-level diagram of Er3+ and Tm3+ ions. (C) 2008 Optical Society of America

Cr^3＋：Al2O3透明多晶陶瓷光谱特性分析

对透光性良好的Cr^3＋：Al2O3透明多晶陶瓷的光谱性能进行了研究，其吸收光谱中吸收峰与单晶红宝石相一致，按吸收光谱和Tanabe-Sugano能级图，算出其晶场强度参数Dq及Racah参数B分别为1792cm^-1，689cm^-1，Dq／B=2．6，陶瓷中Cr^3＋离子所处格位的晶体场强比单晶弱一些，但Cr^3＋：Al2O3透明陶瓷仍属于强场晶体材料；当Cr^3＋掺杂浓度到达0．8wt％时，陶瓷的发射谱仍保持较好的R线发射；随Cr^3＋掺杂浓度的增大，激发峰位发生“红移”．在Cr^3＋：Al2O3透

铝酸镧单晶体中Ce^3＋的能级结构和荧光特性

采用提拉法成功生长了纯LaAlO3和掺铈的LaAlO3单晶体，测试了它们的远红外吸收谱，紫外吸收谱，荧光谱，根据吸收光谱确定了晶体中Ce^3+的能级结构，利用这一能级结构模型较好地解释了Ce：LaAlO3晶体的荧光光谱。

利用窄得-奥菲特理论研究Tm:Lu_2SiO_5晶体的光谱特性

采用丘克拉斯基(Czochralski)技术生长了掺铥硅酸镥(Tm∶Lu2SiO5,Tm∶LSO)晶体;测量了LSO晶体在室温下的非偏振吸收光谱和非偏振荧光光谱;利用窄得-奥菲特(Judd-Ofelt)理论计算了Tm∶LSO晶体的窄得-奥菲特强度参数、振子强度、自发辐射概率、辐射寿命、积分吸收截面和积分发射截面.Tm∶LSO晶体的强度参数为Ω2=9.1355×10-20cm2,Ω4=8.4103×10-20cm2,Ω6=1.5908×10-20cm2;Tm∶LSO晶体在1.9μm附近有明显的发射峰(3F4→3H6跃迁),相应的辐射寿命为2.03 ms,积分发射截面为5.81×10-18cm2,半峰全宽(FWHM)为250 nm.用Tm∶LSO晶体在77 K温度下实现了激光运转.利用792 nm的激光二极管(LD)作为抽运源,获得中心波长为1960 nm的激光输出,抽运阈值为2.13 kW/cm2.

吡唑啉衍生物有机电致发光器件中激基复合物的发射

以两种吡唑啉衍生物为空穴传输材料(HTM)和BBOT为电子传输材料组成双层器件，获得了相对于组成材料的荧光光谱红移和宽化的电致发光．双层器件和HTM：BBOT等摩尔混蒸薄膜的光致发光及电致发光测量表明，该谱带来自HTM／BBOT界面激基复合物的发射，根据器件的能级图，激基复合物的类型为BBOT的激发态BBOT^

Hole-Phonon Relaxation and Photocatalytic Properties of Titanium Dioxide and Zinc Oxide: First-Principles Approach

First-principles calculations for the temporal characteristics of hole-phonon relaxation in the valence band of titanium dioxide and zinc oxide have been performed. A first-principles method for the calculations of the quasistationary distribution function of holes has been developed. The results show that the quasistationary distribution of the holes in TiO2 extends to an energy level approximately 1eV below the top of the valence band. This conclusion in turn helps to elucidate the origin of the spectral dependence of the photocatalytic activity of TiO2. Analysis of the analogous data for ZnO shows that in this material spectral dependence of photocatalytic activity in the oxidative reactions is unlikely.

Magnetotunnelling spectroscopy: an experimental tool for studying chaos in quantum transport

Resonant tunnelling spectroscopy is used to investigate the energy level spectrum of a wide potential well in the presence of a large magnetic field oriented at angles θ between 0° and 90° to the normal to the plane of the well. In the tilted field geometry, the current-voltage characteristics exhibit a large number of quasiperiodic resonant peaks even though the classical motion of electrons in the potential well is chaotic. The voltage range and spacing of the resonances both change dramatically with θ. We give a quantitative explanation for this behaviour by considering the classical period of unstable periodic orbits within the chaotic sea of the potential well.

Strong carrier lifetime enhancement in GaAs nanowires coated with semiconducting polymer.

The ultrafast charge carrier dynamics in GaAs/conjugated polymer type II heterojunctions are investigated using time-resolved photoluminescence spectroscopy at 10 K. By probing the photoluminescence at the band edge of GaAs, we observe strong carrier lifetime enhancement for nanowires blended with semiconducting polymers. The enhancement is found to depend crucially on the ionization potential of the polymers with respect to the Fermi energy level at the surface of the GaAs nanowires. We attribute these effects to electron doping by the polymer which reduces the unsaturated surface-state density in GaAs. We find that when the surface of nanowires is terminated by native oxide, the electron injection across the interface is greatly reduced and such surface doping is absent. Our results suggest that surface engineering via π-conjugated polymers can substantially improve the carrier lifetime in nanowire hybrid heterojunctions with applications in photovoltaics and nanoscale photodetectors.