三角对称晶场下d8电子组态的EPR参量的普遍公式及其应用

本文考虑到d⁸电子组态中所有自旋三重态和自旋单态对基态的影响,用高阶微扰法导出了d⁸电子组态在三角对称晶场下光谱和基态EPR普遍公式。发现在三角对称晶场下,d⁸电子组态离子的g_⊥ > g_‖或g_⊥ < g_‖和D > 0或D < 0是以立方对称晶场为界,晶体中顺磁离子的配体沿C₃轴伸长或压缩所致。利用所得公式计算了NiCl₂和NiSiF₆·6H₂O晶体的EPR参量,其结果与实验吻合较好。     

Infrared diode laser spectroscopy of O2–N2O van der Waals complex in the ν1 symmetric stretch region of N2O

The rovibrational spectrum of O₂–N₂O van der Waals complex is measured in the v₁ symmetric stretch region of N₂O monomer using a tunable diode laser spectrometer. The complex is generated by a slit-pulsed supersonic expansion with gas mixtures of O₂, N₂O, and He. Both a- and b-type transitions are observed. The effective Hamiltonian for an open-shell complex consisting of a diatomic molecule in a ³Σ electronic state and a closed-shell partner is used to analyze the observed spectrum. Molecular constants in the vibrationally excited state are determined accurately. The band-origin of the spectrum is determined to be 1284.7504(25) cm^-1, red-shifted from that of the N₂O monomer by ～ 0.1529 cm^-1.     

Investigation on the Cs 6S1/2 to 7D electric quadrupole transition via monochromatic two-photon process at 767 nm

We experimentally demonstrate the cesium electric quadrupole transition from the 6S_1/2 ground state to the 7D_3/2,5/2 excited state through a virtual level by using a single laser at 767 nm. The excited state energy level population is characterized by varying the laser power, the temperature of the vapor, and the polarization combinations of the laser beams. The optimized experimental parameters are obtained for a high resolution transition interval identification. The magnetic dipole coupling constant A and electric quadrupole coupling constant B for the 7D_3/2,5/2 states are precisely determined by using the hyperfine levels intervals. The results, A = 7.39 (0.06) MHz, B = −0.19 (0.18) MHz for the 7D_3/2 state, and A = −1.79 (0.05) MHz, B =1.05 (0.29) MHz for the 7D_5/2 state, are in good agreement with the previous reported results. This work is beneficial for the determination of atomic structure information and parity non-conservation, which paves the way for the field of precision measurements and atomic physics.     

Solid-state electrochemical CO2 sensor by coupling lithium ion conductor (Li2CO3-Li3PO4-Asl2O3) with oxide ion-electron mixed conductor (La0.9Sr0.1MnO3)

A solid-state electrochemical cell of the type O₂(air), PtLa_0.9Sr_0.1MnO₃/Li₂CO₃(+5 mol% Li₃PO₄ + 6 mol% Al₂O₃)/Au, CO₂, O₂ was composed to determine CO₂ concentration, where Li₂CO₃, a lithium ion conductor, was used as an electrolyte, and the perovskite-type oxide (La_0.9Sr_0.1MnO₃)/O₂-electrode as a reference electrode. The electromotive force (EMF) of the cell was found to be proportional to the logarithm of CO/₂ partial pressure in CO₂/O₂/N₂ gas mixtures at temperatures between 300 and 400 °C. The EMF responded to changes of CO₂ partial pressure within 1 min at 400 °C. The sensitivity to CO₂ of this cell was not affected by coexistence of O₂, and the EMF remained constant after the first 15 days. The mechanism for sensing CO₂ is discussed.     

Effects of surface treatments and annealing on carbon-based molecular sieve membranes for gas separation

A new method in preparing carbon-based molecular sieve (CMS) membranes for gas separation has been proposed. Carbon-based films are deposited on porous Al₂O₃ disks using hexamethyldisiloxane (HMDSO) by remote inductively coupled plasma (ICP) chemical vapor deposition (CVD). After treating the film with ion bombardment and subsequent pyrolysis at a high temperature, carbon-based molecule sieve membranes can be obtained, exhibiting a very high H₂/N₂ selectivity around 100 and an extremely high permeance of H₂ around 1.5 × 10⁻⁶ mol m⁻² s⁻¹ Pa⁻¹ at 298 K. The O₂/N₂ selectivity could reach 5.4 with the O₂ permeance of 2 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ at 423 K.

During surface treatments, HMDSO ions were found to be more effective than CH₄, Ar, O₂ and N₂ ions to improve the selectivity and permeance. Short and optimized surface treatment periods were required for high efficiency. Without pyrolysis, surface treatments alone greatly reduced the H₂ and N₂ permeances and had no effect on the selectivity. Besides, without any surface treatment, pyrolysis alone greatly increased the H₂ and N₂ permeances, but had no improvement on the selectivity, owing to the creation of large pores by desorption of carbon. A combination of surface treatment and pyrolysis is necessary for simultaneously enhancing the permeance and the selectivity of CMS membranes, very different from the conventional pore-plugging mechanism in typical CVD.     

A laboratory study of the 8.65 μm fundamental of CH3D at temperatures relevant to titan''s atmosphere

Spectral transmittance measurements have been performed in the v₆-fundamental of ¹²CH₃D at 153 K. Relevant to the studies of the emission spectra of Titan recorded by the IRIS instruments on board Voyagers 1 and 2, N₂ has been used as the broadening gas. Excellent agreement between experimental and theoretical spectral transmittance has been the result of using N₂-broadened line widths and their dependence upon temperature measured by us in the v₂-fundamental and S = 63.6 cm^-2 atm^-1 for the absolute intensity of the v₆-fundamental.     

Minimum structure of high-harmonic spectrafrom aligned O2 and N2 molecules

We experimentally investigated the high-order harmonic generation (HHG) from aligned O₂ and N₂ molecules in a linearly polarized laser field, and presented the dependence of the harmonic spectrum on the driving laser intensity and molecular alignment angle. The minimum position of HHG of O₂ varies with changing the laser intensity, which is caused by multi-orbital interference. However, the location of the observed minimum structure in N₂ harmonic spectrum remained unchanged upon changing the laser intensity. The mechanism of the spectral minimum for N₂ case is regarded as a Cooper-like minimum in HHG associated with the molecular electronic structure. This work indicates that harmonic spectroscopy can effectively uncover information about molecular structure and electron dynamics.     

共焦腔增强的空气拉曼散射

拉曼光谱是一种无损、快速的物质成分分析和检测方法.由于拉曼信号强度微弱,使得拉曼光谱的检测应用受到极大的限制.针对增强拉曼散射信号强度、提高检测灵敏度这一问题,设计了一种用于自发拉曼散射信号增强的共焦腔样品池,开展了基于该共焦腔的空气拉曼散射信号增强研究.共焦腔的腔镜反射率为92%,这一设计在保证共焦腔通带宽度与激光器线宽匹配的同时能有效地降低共振调节难度.实验中采用0°探测构型收集拉曼信号,并由成像式拉曼光谱仪获取光谱信号.实验发现,在共振状态下,共焦腔的耦合效率达到87.5%,单向激光功率实现约11倍放大;与无共振腔相比,共焦腔对拉曼信号实现17倍放大,信噪比提高2倍.此外,空气中CO_2的3σ检测限达到200 ppm量级.结果表明,该系统对自发拉曼散射信号增强效果显著,并且有较高的检测灵敏度.     

~6Li原子跃迁频率和超精细分裂的精密测量

本文实现了可用于锂原子频率精密测量的冷原子系统,获得了大数目的原子样品;利用西西弗斯冷却和速度选择相干布居俘获实现了~6Li的冷原子的灰色黏胶冷却,原子的温度被冷却到多普勒冷却极限以下,达到50μK;利用光学频率梳,实验上测量了D1线的跃迁频率和超精细分裂,测量结果和理论计算相接近,可以和目前最精确的测量相比较.这些测量为进一步的轻质量原子频率的精密测量、α常数以及核半径的精确标定打下了基础.     

1.39 μm附近H2O谱线参数测量及其在燃烧动力学中的应用

将可调谐半导体激光吸收光谱技术应用于高温气体浓度在线检测,谱线参数的准确性非常重要。为利用红外波段进行燃烧生成H₂O的浓度在线测量,需要实验校准H₂O的谱线参数,尤其是Ar加宽系数,该系数对燃烧反应速率测量和机理验证至关重要。采用半导体激光器作为光源,结合实验室搭建的谱线参数测量系统,采集了1.39 μm波段附近H₂O的4条吸收谱线信号,获得了谱线线强、自加宽系数和N₂加宽系数,与HITRAN数据库和文献结果进行了对比,均吻合较好。首次系统地获得了该波段谱线的Ar加宽系数。在谱线参数确定基础上,获得了在反射激波高温条件下H₂/O₂/Ar燃烧生成H₂O的浓度随时间的演变曲线,验证了相应燃烧动力学机理。结果为利用该波段进行含氢燃料燃烧过程H₂O浓度测量及相关高温燃烧动力学研究提供了可靠的实验依据。     

Proton polarization observables for the elastic and inelastic scattering of 500 MeV protons from Ca and Pb

Measurements for the elastic and inelastic scattering of 500 MeV protons from ⁴⁰Ca and ²⁰⁸Pb at small momentum transfers are reported. The induced proton polarization P and the spin rotation parameter Q were measured for the elastic scattering. The spin rotation parameters D_SS′, D_SL′, D_LL′, d_LS′ and the induced polarization P were measured for transitions to the 3⁻(3.37 MeV) and 5⁻(4.48 MeV) states in ⁴⁰Ca and the 3⁻(2.61 MeV) state in ²⁰⁸Pb. Comparisons of the data with the theoretical calculations were carried out in the framework of nonrelativistic and relativistic approaches. We extracted the spin-up and spin-down channels for the elastic scattering cross sections and found that predictions of the relativistic and nonrelativistic approaches agree well with the spin-up channel data and differ considerably in the spin-down channel.     

The effect of hydrogen on copper nitride thin films deposited by magnetron sputtering

Copper nitride thin films were deposited on Si (1 0 0) wafers by reactive magnetron sputtering at various H₂/N₂ ratios. X-ray diffraction measurements show that the films are composed of Cu₃N crystallites with anti-ReO₃ structure and exhibit preferred orientation of [1 0 0] direction. Although the relative composition of the films has obviously changes with the H₂/N₂ ratios, the orientations of the films keep almost no changes. However, the grain size, lattice parameter and composition of the films are strongly dependent on the H₂/N₂ ratios. The copper nitride films prepared at 10% H₂/N₂ ratios show poor stability and large weight gain compared to the copper nitride films prepared at 0% H₂/N₂ ratios.     

超声喷流氩氢混合团簇特性研究

利用瑞利散射方法研究了超声喷流Ar-CH4混合团簇和超声喷流Ar-H2混合团簇的特性.通过测量不同混合比例和不同背压下所形成混合团簇的散射信号发现,当用Ar气和CH4的混合气体进行超声喷流时很容易形成Ar-CH4混合团簇,当Ar气含量为50%时混合团簇尺度最大且大于相同气压下纯Ar团簇尺度和纯CH4团簇尺度.实验发现,与纯H2团簇只能在低温条件下获得不同,常温下即可形成Ar-H2混合团簇,实现了常温下含氢团簇的获取,从而有效降低了制备成本.在H2含量大于40%时混合团簇开始形成并在60%时达到最大尺度.含氢(氘)混合团簇在氢(氘)团簇的基础上引入了更重的异核Ar元素,在激光氘团簇聚变实验中它将进一步加速氘离子从而获得更高的能量,并具有更高的中子产额和聚变效率.     

Electrons and holes in undoped Nd2CuO4

Nd₂CuO_4±δ is the non-superconducting prototype of the Re_2−xM_xCuO₄t−y family (Re=Pr, Nd, Sm and M=Ceor Th) of n-type oxide superconductors. Four-probe DC conductivity, EMF in P(O₂) gradient, and thermopower measurements have been used to characterise its electric transport and defect structure between 300 and 900°C and between 5×10⁻⁴ and 1 atm oxygen partial pressure.

The results show that Nd₂CuO_4±δ can be oxygen under-stoichiometric (with n-type conductivity), near-stoichiometric, and over-stoichiometric (with p-type conductivity) in different T, P(O₂) ranges.     

Oxygen diffusion and surface exchange in La1−xSrxFe0.8Cr0.2O3−δ (x=0.2, 0.4 and 0.6)

Oxygen tracer diffusion (D*) and surface exchange rate constant (k*) have been measured, using isotopic exchange and depth profiling by secondary ion mass spectrometry (SIMS), in La_1−xSr_xFe_0.8Cr_0.2O_3−δ (x=0.2, 0.4 and 0.6). Measurements were made as a function of temperature (700–1000 °C) and oxygen partial pressure (0.21–10⁻²¹ atm) in dry oxygen, water vapour and water vapour/hydrogen/nitrogen mixtures. At high oxygen activity, D* was found to increase with increasing temperature and Sr content. The activation energies for D* in air are 2.13 eV (x=0.2), 1.53 eV (x=0.4) and 1.21 eV (x=0.6). As the oxygen activity decreases, D* increases as expected qualitatively from the increase in oxygen vacancy concentration. Under strongly reducing conditions, the measured values of D* at 1000 °C range from 10⁻⁸ cm² s⁻¹ for x=0.2 to 10⁻⁷ cm² s⁻¹ for x=0.4 and 0.6. The activation energies determined at constant H₂O/H₂ ratio are 1.21 eV (x=0.2), 1.59 eV (x=0.4) and 0.82 eV (x=0.6).

The surface exchange rate constant of oxygen for the H₂O molecule is similar in magnitude to that for the O₂ molecule and both increase with increasing Sr concentration.     

Development of a laser-based Raman scattering system for identifying and quantifying major gas species

The construction of a laser-based Raman scattering system for identifying major gas species and quantifying their partial pressures is described. The system incorporates a pulsed laser to minimize the background luminescence. The results obtained at room temperature for N₂ at (365·80·5) nm and for O₂ at (355·80·5) nm are presented.     

A Correlation Potential Method for Electron Scattering Total Cross Section Calculations on Several Diatomic and Polyatomic Molecules over Energy Range 10 ～ 5000 eV

A complex optical model potential correlated by the concept of bonded atom, which considers the overlapping effect of electron clouds between two atoms in a molecule, is firstly employed to calculate the total cross sections for electron scattering on several molecules (NH₃, H₂O, CH₄, CO, N₂, O₂, and C₂H₄) over the energy range 10～5000 eV using the additivity rule model at Hartree-Fock level. The difference between the bonded atom and the free one in states is that the overlapping effect of electron clouds of bonded atoms in a molecule is considered. The quantitative total cross sections are compared with the experimental data and with the other calculations wherever available and good agreement is obtained over the energy range 10～5000 eV. It is shown that the correlated calculations are much closer to the available experimental data than the uncorrelated ones at lower energies, especially below 500 eV. Therefore, considering the overlapping effect of electron clouds in the complex optical model potential could be helpful for the better accuracy of the total cross section calculations of electron scattering from molecules.     

SeN_2自由基解析势能函数的耦合簇理论研究

利用单双迭代耦合簇理论CCSD结合相关一致四重基组cc-pVQZ对SeN2基态的平衡结构和谐振频率进行了优化计算.计算结果表明:基态SeN2自由基分子稳定态为C2v构型,基态电子组态为X1A1,平衡核间距RSe-N=0.1691 nm,RN-N=0.1970 nm,αN-Se-N=71.289?,离解能De=4.78 eV.基态简正振动频率分别为:ν1=326.9288 cm-1,ν2=808.0161 cm-1以及ν3=948.3430 cm-1.对SeN基态和N2基态采用上述相同方法进行几何构型与谐振频率的计算并进行单点能扫描,使用Murrell-Sorbie函数进行最小二乘拟合得到其势能函数和光谱常数,通过和其他理论值以及实验值做比较,显示本文的计算工作达到了很高的精度.应用多体项展式理论导出了基态SeN2的全空间解析势能函数,其势能函数等值势能图准确再现了SeN2分子的结构特征和能量变化.     

D-T2二维核磁共振脉冲序列及反演方法改进设计

面对日益复杂的勘探对象, D-T₂二维核磁共振技术在实际应用中面临无法兼顾扩散系数测量范围和横向弛豫分辨率的困境. 脉冲序列作为D-T₂二维核磁共振数据采集的核心技术, 其性能优劣直接影响应用效果, 在综合对比PFG, STE-PFG, BP-PFG、改良式CPMG, 扩散编程, 多回波间隔CPMG脉冲序列性能的基础上, 有效融合脉冲梯度场、恒定梯度场D-T₂脉冲序列的优点, 本文提出一种基于脉冲梯度场的双变量、两窗口D-T₂脉冲序列改进设计. 针对两个窗口的D-T₂二维核磁共振数据反演, 为突破现有反演方法无法兼顾反演精度和解谱效率的瓶颈, 本着第二个窗口回波信号为主、第一个窗口回波信号为辅的原则, 本文提出一种同时使用两个窗口数据参与解谱的联合TSVD反演方法. 气水、油水、稠油、油气水模型不同信噪比条件下的数值模拟结果表明, 本文提供的D-T₂改进脉冲序列达到了平衡扩散系数测量范围和横向弛豫分辨率的设计要求, 本文提供的联合TSVD反演方法也有效平衡了反演精度要求和解谱效率. 文中的D-T₂改进脉冲序列及联合TSVD反演方法在复杂油气藏流体识别和产能预测中具有广泛的应用前景, 可为促进国内D-T₂二维核磁共振岩心分析技术的发展提供有利条件.