气相中Fe+催化CO与N2O循环反应的理论计算研究

采用密度泛函UB3LYP/6–311+G(2d)方法计算研究了Fe+在基态和激发态与CO与N2O反应的反应机理。全参数优化了反应势能面上各驻点的几何构型,用频率分析方法和内禀反应坐标（IRC）方法对过渡态进行了验证,并用UB3LYP/6–311++G(3df,3pd)、单点垂直激发等方法分别进行各驻点单点能校正,四重态和六重态反应势能面交叉点CP确定,计算结果表明,该反应为两步反应,且反应机理都为插入—消去反应,势能面上的两个交叉点能够有效的降低反应的活化能,这在动力学和热力学上都是有利的。     

Second-order random wave solutions for interfacial internal waves in N-layer density-stratified fluid

This paper studies the random internal wave equations describing the density interface displacements and the velocity potentials of N-layer stratified fluid contained between two rigid walls at the top and bottom. The density interface displacements and the velocity potentials were solved to the second-order by an expansion approach used by Longuet-Higgins （1963） and Dean （1979） in the study of random surface waves and by Song （2004） in the study of second- order random wave solutions for internal waves in a two-layer fluid. The obtained results indicate that the first-order solutions are a linear superposition of many wave components with different amplitudes, wave numbers and frequencies, and that the amplitudes of first-order wave components with the same wave numbers and frequencies between the adjacent density interfaces are modulated by each other. They also show that the second-order solutions consist of two parts： the first one is the first-order solutions, and the second one is the solutions of the second-order asymptotic equations, which describe the second-order nonlinear modification and the second-order wave-wave interactions not only among the wave components on same density interfaces but also among the wave components between the adjacent density interfaces. Both the first-order and second-order solutions depend on the density and depth of each layer. It is also deduced that the results of the present work include those derived by Song （2004） for second-order random wave solutions for internal waves in a two-layer fluid as a particular case.     

Influence of annealing conditions on impurity species in arsenic-doped HgCdTe grown by molecular beam epitaxy

Based on our previous work,the influence of annealing conditions on impurity species in in-situ arsenic (As)-doped Hg 1 x Cd x Te (x ≈ 0.3) grown by molecular beam epitaxy has been systematically investigated by modulated photoluminescence spectra.The results show that (i) the doped-As acting as undesirable shallow/deep levels in as-grown can be optimized under proper annealing conditions and the physical mechanism of the disadvantage of high activation temperature,commonly assumed to be more favourable for As activation,has been discussed as compared with the reports in the As-implanted HgCdTe epilayers (x ≈ 0.39),(ii) the density of V Hg has an evident effect on the determination of bandgap (or composition) of epilayers and the excessive introduction of V Hg will lead to a short-wavelength shift of epilayers,and (iii) the V Hg prefers forming the V Hg-As Hg complex when the inactivated-As (As Hg or related) coexists in a certain density,which makes it difficult to annihilate V Hg in As-doped epilayers.As a result,the bandedge electronic structures of epilayers under different conditions have been drawn as a brief guideline for preparing extrinsic p-type epilayers or related devices.     

Synthesis and Crystal Structure of New Thiazolyl-Pyrazoline Derivatives Bearing 1,2,4-Triazole Moiety

Abstract  

The title compounds 1-(4-aryl-5-triazolyl-2-thiazolyl)-3,5-diaryl-2-pyrazoline derivatives (3a–c) were synthesized by reacting 3,5-diaryl1-thiocarbamoyl -2-pyrazoline 1 with 2-bromo-1-aryl-2-(1H-1,2,4-triazol-1-yl) ethanones 2 in boiling ethanol. Their structures were characterized by IR, ¹H-NMR, MS spectroscopic data and elementary analyses. The structure of compound (3a), C₂₆H₁₈Cl₂N₆S, was conclusively established with X-ray crystal structure analysis. It crystallizes in the Orthorhombic space group Pna2(1), with a = 17.8160(5), b = 18.9125(7), c = 14.7926(4), α = 90°, β = 90°, γ = 90°and Dc = 1.379 mg/m³ for Z = 8, V = 4984.3(3) ?, μ(Mo–Kα) = 0.372 mm, λ = 0.71070 ?, the final R = 0.0527 and wR = 0.1307 for 43309 observed reflections with I > 2σ(I). The structure is stabilized by weak C–H···N intramolecular hydrogen bonds and C–H···Cg p-ring intermolecular interactions and gives support to molecular packing stability in the unit cell.     

Persistence properties and wave‐breaking criteria for the Geng‐Xue system

Considered herein is a two‐component Novikov equations (called Geng‐Xue system for short) with cubic nonlinearities. The persistence properties and some unique continuation properties of the solutions to the system in weighted L_p spaces are established. Moreover, a wave‐breaking criterion for strong solutions is determined in the lowest Sobolev space by using the localization analysis in the transport equation theory, and we also give a lower bound for the maximal existence time.     

Multifunctional land‐use value mapping and space type classification: A case study of Puge County,China

Land exhibits diverse functions under the combined influence of natural and human forces. A production–living–ecology functional classification system was constructed by integrating land, ecosystem, and landscape functions. The land functional value was calculated by systematically integrating ecosystem service value assessments. The primary and secondary functions, as well as combinations of different land‐use types, were determined using vertical and horizontal comparison methods. The production–living–ecology ranges were then delineated in Puge County, which is a typical mountain county in China. The production–living–ecology functions identified were well connected with the current land‐use types. The “production–living–ecology” space in Puge County showed obvious multifunctionality and agglomeration. The function identification system proposed in this paper integrated multiple methods, overcame the difficulty of direct quantitative identification of land functions. The methods used to map and quantify land function will enhance our ability to understand and model land system changes and adequately inform policies and planning. Summary for Managers

• The function valuation method constructed in this paper could be used to reflect the multifunctionality and importance of land use and provide guidance and a quantitative basis for regional development planning.
• The spatial classification results provided in this paper could offer a valuable reference for the land management department to scientifically formulate land use planning.
• Under the goal of creating a group‐type urban development pattern and constructing an ecological protection pattern in Puge County, the hotspot analysis results of this paper can provide decision‐making tools and alternative spatial plans.

     

Intermolecular interactions between natural humic substances and tricyclic antidepressants

1. Download : Download high-res image (128KB)
2. Download : Download full-size image

     

Catalyst-controlled diastereoselective ring-opening formal [3+2]-cycloadditions of arylvinyl oxirane 2,2-diesters with cyclic N-sulfonyl imines

A diastereoselectivity-controllable formal [3+2]-cycloaddition of arylvinyl oxirane 2,2-diesters with cyclic N-sulfonyl imines is developed, affording the corresponding tricyclic oxazolidine derivatives in moderate to excellent yields with excellent diastereoselectivities in the presence of palladium(0) or scandium(III) triflate. This protocol allows selective synthesis of diastereomers of tricyclic oxazolidine derivatives under switchable and mild conditions. Further transformations of the obtained products were conducted by removing ester groups and arylvinyl moieties.     

Molecular insight into structures of monocationic and dicationic ionic liquids in mica slits

Structures of ionic liquids (ILs) 1-decyl-3-methylimidazolium bis(trifluoromethanesulfonyl)azanide ([C₁₀mim][TFSA]) and 1-decyl-dimethylimidazolium bis(trifluoromethanesulfonyl)azanide ([C₁₀(mim)₂](TFSA)₂) in different-sized mica slits have been investigated using molecular dynamics simulations. Ion density and angular distributions for monocationic IL [C₁₀mim][TFSA] were analysed to elucidate the IL structures under different surface charges and especially their changes in the direction perpendicular to the surfaces. [C₁₀mim][TFSA] formes in bilayers, compatible with existing models of ILs with long alkyl chains. For dicationic IL [C₁₀(mim)₂](TFSA)₂, cations adjacent to the mica surface tend to stay parallel to the surface with both positively charged rings absorbed. While near the centre of the slit, dications show the weak tendency of orientation distribution, more random than [C₁₀mim]⁺ ions. Structures of [C₁₀(mim)₂](TFSA)₂ cannot be described by bilayer models. Additionally, the in-plane arrangement of [C₁₀mim][TFSA] is more ordered when K⁺ ions completely neutralise the negative charge of the mica surface, and [C₁₀mim]⁺ ions tend to be located in hexagonal mica lattices with two aluminium atoms in replacement of silicon atoms. [TFSA]^? ions are constrained by the neighbouring K⁺ ions absorbed onto mica lattices.