Spectroscopic investigations on NO+(x1∑+,a3∑+,A1Ⅱ) ion using multi-reference configuration interaction method and correlation-consistent sextuple b

Three low-lying electronic states (x¹∑⁺,a³∑⁺,and A¹Ⅱ) of NO⁺ ion are studied using the complete active space self-consistent-field (CASSCF) method followed by highly accurate valence internally contracted multi-reference configuration interaction (MRCI) approach in combination of the correlation-consistent sextuple basis set augmented with diffuse functions, aug-cc-pV6Z. The potential energy curves (PECs) of the NO⁺(x¹∑⁺,a³∑⁺,A¹Ⅱ) are calculated. Based on the PECs, the spectroscopic parameters R_e, D_e, ω_e, ω_eχ_e, α _e, B_e, and D₀ are reproduced, which are in excellent agreement with the available measurements. By numerically solving the radial Schrödinger equation of nuclear motion using the Numerov method, the first 20 vibrational levels, inertial rotation and centrifugal distortion constants of NO⁺(x¹∑⁺,a³∑⁺,A¹Ⅱ) ion are derived when the rotational quantum number J is equal to zero (J = 0) for the first time, which accord well with the available measurements. Finally, the analytical potential energy functions of these states are fitted, which are used to accurately derive the first 20 classical turning points when J = 0. These results are compared in detail with those of previous investigations reported in the literature.     

Ni/α-Al2O3催化剂作用下苯甲醚的加氢脱氧

Ni-based catalysts supported on di erent supports (α-Al₂O₃,γ-Al₂O₃, SiO2, TiO₂, and ZrO₂) were prepared by impregnation. Effects of supports on catalytic performance were tested using hydrodeoxygenation reaction (HDO) of anisole as model reaction. Ni/α-Al₂O₃ was found to be the highest active catalyst for HDO of anisole. Under the optimal conditions, the anisole conversion is 93.25% and the hydrocarbon yield is 90.47%. Catalyst characteriza-tion using H₂-TPD method demonstrates that Ni/α-Al₂O₃ catalyst possesses more amount of active metal Ni than those of other investigated catalysts, which can enhance the cat-alytic activity for hydrogenation. Furthermore, it is found that the Ni/α-Al₂O₃ catalyst has excellent repeatability, and the carbon deposited on the surface of catalyst is negligible.     

Low temperature laser absorption spectra of methane in the near-infrared at 1.65 μm for lower state energy determination

Direct absorption spectra of the 2v₃ band of methane (CH₄) from 6038 to 6050 cm^-1 were studied at different low temperatures using a newly developed cryogenic cell in combination with a distributed feedback (DFB) diode laser. The cryogenic cell can operate at any stabilized temperature ranging from room temperature down to 100 K with temperature fluctuation less than ±1 K within 1 hour. In the present work, the CH₄ spectra in the range of 6038-6050 cm^-1 were recorded at 296, 266, 248, 223, 198, and 176 K. The lower state energy E″ and the rotational assignment of the angular momentum J were determined by a “2-low-temperature spectra method” using the spectra recorded at 198 and 176 K. The results were compared with the data from the GOSAT and the recently reported results from Campargue and co-workers using two spectra measured at room temperature and 81 K. We demonstrated that the use of a 2-low-temperature spectra method permits one to complete the E″ and J values missed in the previous studies.     

Investigations of spectroscopic parameters and molecular constants for X1Σg+, w3Δu, and W1Δu electronic states of P2 molecule

The potential energy curves (PECs) of three low-lying electronic states (X¹Σ_g⁺, w³Δ_u, and W¹Δ_u)of P₂ molecule are investigated using the full valence complete active space self-consistent field (CASSCF) method followed by the highly accurate valence internally contracted multireference configuration interaction (MRCI) approach in conjunction with the correlation-consistent basis set in the valence range. The PECs of the electronic states involved are modified by the Davidson correction and extrapolated to the complete basis set (CBS) limit. With these PECs, the spectroscopic parameters of the three electronic states are determined and compared in detail with the experimental data. The comparison shows that excellent agreement exists between the present results and the available experimental data. The complete vibrational states are computed for the w³Δ_u, and W¹Δ_u electronic states when the rotational quantum number J equals zero and the vibrational level G(v), the inertial rotation constant B_v, and the centrifugal distortion constant D_v of the first 30 vibrational states are reported, which accord well with the experimental data. The present results show that the two-point extrapolation scheme can obviously improve the quality of spectroscopic parameters and molecular constants.     

Structures and luminescence properties of Yb3＋ in the double perovskites Ba2YB＇O6 （B＇=Ta5＋, Nb5＋） phosphors

The Yb³⁺ doped Ba₂YB'O₆ (B'=Ta⁵⁺, Nb⁵⁺) were prepared by high temperature solid-state reaction method, their structures were determined by x-ray diffraction and refined by Rietveld method. The diffuse reflection absorption, excitation and emission spectra of Yb³⁺:Ba₂YB'O₆ (B'=,Ta⁵⁺, Nb⁵⁺) were measured at room temperature. Under the excitation of ultraviolet light, these phosphors exhibit broad charge transfer band emissions of TaO₆ or NbO₆ centre with large Stokes shift. The Yb³⁺ doped into these hosts are situated at Y³⁺ sites of cubic symmetry (O_h). The experimental energy levels of Yb³⁺ in Ba₂YTaO₆ and Ba₂YNbO₆ were determined by photoluminescence and diffuse reflection absorption spectra. Their wavefunctions and theoretical energy levels were obtained by diagonalising the Hamiltonian matrix. The experimental energy levels were fitted by Levenberg--Marquardt iteration algorithm to determine crystal field parameters. Then, the magnetic-pole transition line strengths of Yb³⁺:Ba₂YB'O₆(B'=Ta⁵⁺, Nb⁵⁺) from (²F_5/2)Γ₈^- to the low-energy states were calculated.     

Ar原子偶宇称3p5(2P1/2)nl'[K']J(l'=1,3)自电离态激发谱线形研究

The even-parity autoionizing resonance series 3p⁵np''[3/2]_1,2, 3p⁵np''[1/2]₁, and 3p⁵nf''[5/2]₃ of Ar have been investigated exciting from the two metastable states 3p⁵4s[3/2]₂ and 3p⁵4s''[1/2]₀ in the photon energy range of 32500-35600 cm^-1 with an experimental bandwidth of ~0.1 cm^-1. The excitation spectra of the even-parity autoionizing resonance series show typical asymmetric line shapes. New level energies, quantum defects, line profile index and resonance widths, resonance lifetime and reduced widths of the autoionizing resonances are derived by a Fano-type line-shape analysis. The line profile index q and the resonance widths Γ are shown to be approximately proportional to the effective principal quantum number n^*. The line separation of the 3p⁵np'' autoionizing resonances is discussed.     

Multiferroic properties of solben gel derived Bi5Fe1-xCoxTi3O15 thin films

Co-doped Bi₅FeTi₃O₁₅ thin films (BFCT-x, Bi₅Fe_1-xCo_xTi₃O₁₅) were prepared using a sol—gel technique. XRD patterns confirm their single phase Aurivillius structure, and the corresponding powder Rietveld analysis indicates the change of space group around x=0.12. The magnetic hysteresis loops are obtained and ferromagnetism is therefore confirmed in BFCT-x thin films. The remanent magnetization (M_r) first increases and reaches the maximum value of 0.42 emu/cm³ at x=0.12 due to the possible Fe³⁺—O—Co³⁺ ferromagnetic coupling. When x = 0.25, the M_r increases again because of the dominant Fe³⁺—O—Co³⁺ ferromagnetic coupling. The remanent polarization (2P_r) of BFCT-0.25 was measured to be as high as 62 μC/cm², a 75% increase when compared with the non-doped BFCT-0 films. The 2P_r remains almost unchanged after being subjected to 5.2 × 10⁹ read/write cycles. Greatly enhanced ferroelectric properties are considered to be associated with decreased leakage current density.     

利用原位傅里叶变换红外光谱诊断催化剂的特性和催化活性

The present work establishes a systematic approach based on the application of in-situ Fourier transform infrared spectroscopy (FTIR) for the investigation of the crystal structure, thermal stability, redox behavior (temperature-programmed reduction/temperatureprogrammed re-oxidation) as well as the catalytic properties of Co₃O₄ thin films. The syntheses of Co₃O₄ were achieved by chemical vapor deposition in the temperature range of 400-500℃. The structure analysis of the as-prepared material revealed the presence of two prominent IR bands peaking at 544 cm^-1 (υ₁) and 650 cm^-1 (υ₂) respectively, which originate from the stretching vibrations of the Co-O bond, characteristic of the Co₃O₄ spinel. The lattice stability limit of Co₃O₄ was estimated to be above 650℃. The redox properties of the spinel structure were determined by integrating the area under the emission bands υ₁ and υ₂ as a function of the temperature. Moreover, Co₃O₄ has been successfully tested as a catalyst towards complete oxidation of dimethyl ether below 340 ℃. The exhaust gas analysis during the catalytic process by in situ absorption FTIR revealed that only CO₂ and H₂O were detected as the final products in the catalytic reaction. The redox behavior suggests that the oxidation of dimethyl ether over Co₃O₄ follows a Mars-van Krevelen type mechanism. The comprehensive application of in situ FTIR provides a novel diagnostic tool in characterization and performance test of catalysts.     

高灵敏，高选择和可视化识别Hg2+的罗丹明turn-on型化学传感器

Two novel rhodamine-based fluorescence enhanced molecular probes (RA₁ and RA₂) were synthesized, which were both designed as comparative fluoroionophore and chromophore for the optical detection of Hg²⁺. The recognizing behaviors were investigated both experimentally and computationally. They exhibited high selectivity and sensitivity for Hg²⁺ over other commonly coexistent metal ions in CH₃CN/H₂O (1:1, V/V) solution. Test shows that hydroxy benzene of rich electron was beneficial to the chelate of Hg²⁺ with sensors. The detection limit was measured to be at least 0.14 μmol/L. After addition of Hg²⁺, the color changed from colourless to pink, which was easily detected by the naked eye in both solution and hydrogel sensor.     

Structural features of aluminium alloy 1441 irradiated by Ar+ ions

Using electron microscopy it was found that irradiation of clad cold-worked specimens made of commercial aluminium-lithium alloy 1441 by the Ar ⁺ ions of energy 40 keV at low doses of irradiation (10¹⁵ cm⁻², irradiation time 1 s, T < 70 °C) and ion-current density of about 100 μA/cm² results in the transformation of the cellular structure formed in the alloy under deformation. As the dose of irradiation is increased up to 10¹⁶ cm⁻², a transition from a cellular to a subgrain structure close to a polygonal one is observed. The efficiency of the process is increased with ion-current density. Furthermore, under ion irradiation at increased ion-current densities, the β′(Al ₃ Zr) and Al ₈ Fe ₂ Si particles present in the deformed alloy dissolve, and disperse particles of a new Al ₂ LiMg phase of platelet shape are formed. The changes in the dislocation structure and phase composition in alloy 1441 are observed several seconds after irradiation not only in the surface layer adjacent to the ion incorporation band but also through the thickness of the specimen tens of thousands times greater than ion projective ranges. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 73–81, February, 2007.     

RAMAN SCATTERING OF α-ET3(ReO4)2 CHARGE-TRANSFER SALT

We describe the results of Haman studies on C=C stretch modes in α-ET₃(ReO₄)₂ charge-transfer salt with the incident laser beam polarised perpendicular and parallel to the large flat face of plate-like crystal. We have assigned central C=C stretch mode at 1454 cm^-1 and ring C=C stretch mode at 1470cm^-1. The change in ring C=C stretch vibration was observed at the metal-insulator transition of α-ET₃(ReO₄)₂ on warming due to the distortion of the ET molecules.     

异氰酸分子NH(a1Δ)+CO(X1Σ+)通道在193nm的离子成像光解动力学研究

The photodissociation dynamics of isocyanic acid (HNCO) has been studied by the timesliced velocity map ion imaging technique at 193 nm. The NH(a¹Δ) products were measured via (2+1) resonance enhanced multiphoton ionization. Images have been accumulated for the NH(a¹Δ) rotational states in the ground and vibrational excited state (v=0 and 1). The center-of-mass translational energy distribution derived from the NH(a¹Δ) images implies that the CO vibrational distributions are inverted for most of the measured ¹NH(v|j) internal states. The anisotropic product angular distribution observed indicates a rapid dissociation process for the N-C bond cleavage. A bimodal rotational state distribution of CO(v) has been observed, this result implies that isocyanic acid dissociates in the S₁ state in two different pathways.     

Mg2(BH4)2(NH2)2脱氢机理的理论研究

对Mg₂(BH₄)₂(NH₂)₂的脱氢机理展开系统的理论研究发现相对于分子内的脱氢过程,分子间的脱氢过程在热力学和动力学方面都是比较有利的. Mg₂(BH₄)₂(NH₂)₂脱氢过程的第一步是BH₄^-中的B-H^δ-和NH2-中     

Simulation of near-infrared photodiode detectors based on β-FeSi2/4H-SiC heterojunction

In this paper, we propose the near-infrared p-type β-FeSi₂/n-type 4H-SiC heterojunction photodetector with semiconducting silicide (β-FeSi₂) as the active region for the first time. Optoelectronic characteristics of the photodetector are simulated using a commercial simulator at room temperature. The results show that the photodetector has a good rectifying character and a good response to the near-infrared light. Interface states should be minimized to obtain a lower reverse leakage current. The response spectrum of the β-FeSi₂/4H-SiC detector, which consists of a p-type β-FeSi₂ absorption layer with a doping concentration of 1×10¹⁵ cm^-3 and a thickness of 2.5 μm, has a peak of 755 mA/W at 1.42 μm. The illumination of the SiC side obtains a higher responsivity than that of the β-FeSi₂ side. The results illustrate that the β-FeSi₂/4H-SiC heterojunction can be used as a near-infrared photodetector compatible with near-infrared optically-activated SiC-based power switching devices.     

一氧化二氮分子位于775 nm的6υ3振动泛频跃迁的高精密光腔衰荡光谱

Transitions of the 6υ₃ overtone band of ¹⁴N₂ ¹⁶O near 775 nm have been studied by continuous-wave cavity ring-down spectroscopy. Line positions and intensities were derived from a fit of the line shape using a hard-collisional profile. The line positions determined with absolute accuracy of 5×10^-4 cm^-1 allowed us to reveal finer ro-vibrational couplings taking place after J>14 except a strong anharmonic interaction identified by the effective Hamiltonian model. The absolute line intensities have also been retrieved with an estimated accuracy of 2% for a majority of the unblended lines. A new set of ro-vibrational and dipole moment parameters were derived from the experimental values. A comparison between the line positions and intensities of the 6υ₃ band obtained in this work and those from previous studies is given.     

NO分子b4Σ--a4Πi(4,0)带的吸收光谱

通过对NO与He流动混合气体放电, 产生了激发态的NO(a⁴Π_ii) 分子. 利用光外差-浓度调制吸收光谱技术测量了NO分子在12530-12850 cm^-1波段内的吸收光谱, 并标识出b⁴Σ^--a⁴Π_i(4,0)带在该波段内的324条光谱跃迁谱线. 采用标准⁴Σ^--⁴Π_i哈密顿量模型, 通过非线性最小二乘法拟合其中267条谱线, 拟合残差(0.0071 cm^-1) 接近实验系统测量误差(0.007 cm^-1). 获得的主要分子常数与文献提供的常数符合, 并且拟合得到了精细结构分子常数.     

Scalar-isovector K¯ production close to threshold

The reaction pp → dK ⁺ˉ has been investigated at excess energies Q = 47.4 and 104.7MeV above the K ⁺ˉ threshold at COSY Jülich. Coincident dK⁺ pairs were detected with the ANKE spectrometer, and subsequently ∼ 2000 events with a missing ˉ invariant mass were identified, which fully populate the Dalitz plot. The joint analysis of invariant mass and angular distributions reveals s-wave dominance between the two kaons, in conjunction with a p-wave between the deuteron and the kaon pair, i.e. Kˉ production via the a ₀ ⁺(980) channel. Integration of the differential distributions yields total cross-sections of σ(pp → dK ⁺ˉ) = (38±2_stat±14_syst)nb and (190±4_stat±39_syst)nb for the low and high Q value, respectively.     

Investigation of 4H—SiC metal—insulation—semiconductor structure with Al2O3/SiO2 stacked dielectric

Atomic layer deposited (ALD) Al₂O₃/dry-oxidized ultrathin SiO₂ films as high-k gate dielectric grown on the 8° off-axis 4H-SiC (0001) epitaxial wafers are investigated in this paper. The metal-insulation-semiconductor (MIS) capacitors, respectively with different gate dielectric stacks (Al₂O₃/SiO₂, Al₂O₃, and SiO₂) are fabricated and compared with each other. The I-V measurements show that the Al₂O₃/SiO₂ stack has a high breakdown field ( ≥ 12 MV/cm) comparable to SiO₂, and a relatively low gate leakage current of 1× 10^-7 A/cm² at electric field of 4 MV/cm comparable to Al₂O₃. The 1-MHz high frequency C-V measurements exhibit that the Al₂O₃/SiO₂ stack has a smaller positive flat-band voltage shift and hysteresis voltage, indicating less effective charge and slow-trap density near the interface.     

SIMS STUDY OF OXYGEN SPIRAL DIFFUSION C-TEXTURED Yba2Cu3O7-δ/SrTiO3 EPITAXIAL THIN FILM

Secondary ion mass spectroscopy was used to study the chemical diffusivity of 0¹⁸ in c-textured YBa₂Cu₃O_7-δ/SrTiO₃ epitaxial thin film. By fitting experimental data to the one- dimensional diffusion curve, the apparent diffusivity along the c-axis was obtained to be equal to l.02×10¹⁴cm²/sec when the temperature was 350℃. A computer analysis method was put forward to calculate the "spiral diffusion" process, and the diffusivity anisotopy of films with different mosaic size obtained. For a film of 7000×7000?² mosaic size, Dab was found to be ～3.55×10^-5xexp((-1.03 ev)/kT) cm²/sec. The calculated results reveal that the variation of the results of Dc is not the result of diffusivity anisotropy but of the difference in mosaic size.     

Theoretical study of stereodynamics for the reaction O(3P) +D2 (v=0, j=0) to OD+D and isotope effect

Quasi-classical trajectory (QCT) calculations have been performed to study the product polarization behaviours in the reaction O(³P) + D₂ (v= 0, j= 0)→OD + D. By running trajectories on the ³A′ and ³A″ potential energy surfaces (PESs), vector correlations such as the distributions of the polarization-dependent differential cross sections (PDDCSs), the angular distributions of P(θ_r) and P(ø_r) are presented. Isotope effect is discussed in this work by a comprehensive comparison with the reaction O(³P) + H₂ (v= 0, j= 0) → H + H. Common characteristics as well as differences are discussed in product alignment and orientation for the two reactions. The isotope mass effect differs on the two potential energy surfaces: the isotope mass effect has stronger influence on P(θ_r) and PDDCSs of the ³A′ PES while the opposite on P(ø_r) of the ³A″ potential energy surface.