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61.
采用密度泛函理论方法,在TZ2P-STO基组水平下,对金属四重键化合物M2Cl4(PMe3)4(M=Cr,Mo,W)和Mo2X4(PMe3)4(X=F,Cl,Br,I)的几何结构进行优化,分析了电子结构,并运用TDDFT方法对其低占据激发态进行了计算.考虑相对论效应的ZORA方法能够较好地重现M2X4(PMe3)4的几何结构.M2X4(PMe3)4的电子结构分析表明其d电子的组态为σ^2π^4δ^2,前线轨道能级顺序为πlig〈πd/σd〈δd〈δd^*.金属原子和卤素配体的改变虽然使轨道能量发生变化,但没有影响轨道的排布顺序.TDDFT方法对M2Xa(PMe3)4δd→δd^*和π→δd^*跃迁能量的计算较为准确,对πlig→δd^*(LMCT)跃迁能量的计算误差较大.金属原子、卤素配体以及相对论效应对激发能的影响可以根据分子轨道能级的变化给予解释. 相似文献
62.
Ceramic BaCe0.8Ho0.2O3-α with orthorhombic perovskite structure was prepared by conventional solid state reaction, and its conductivity and ionic transport number were measured by ac impedance spectroscopy and gas concentration cell methods in the temperature range of 600-1000 ℃ in wet hydrogen and wet air, respectively. Using the ceramics as solid electrolyte and porous platinum as electrodes, the hydrogen-air fuel cell was constructed, and the cell performance at temperature from 600-1000 ℃ was examined. The results indicate that the specimen was a pure protonic conductor with the protonic transport number of 1 at temperature from 600-900 ℃ in wet hydrogen, a mixed conductor of proton and electron with the protonic transport number of 0.99 at 1000 ℃. The electronic conduction could be neglected in this case, thus the total conductivity in wet hydrogen was approximately regarded as protonic conductivity. In wet air, the specimen was a mixed conductor of proton, oxide ion and electron hole. The protonic transport numbers were 0.01-0.09, and the oxide-ionic transport numbers were 0.27-0.32. The oxide ionic conductivity was increased with the increase of temperature, but the protonic conductivity displayed a maximum at 900 ℃, due to the combined increase in mobility and depletion of the carriers. The fuel cell could work stably. At 1000 ℃, the maximum short-circuit current density and power output density were 346 mA/cm^2 and 80 mW/cm^2, respectively. 相似文献
63.
A logarithmic expression is proposed to describe relaxation of the polar order in side chain polymers,together with a new way of plotting temperature dependent relaxation data.This results in a straight line extending even below the glass transition temperature in the case of poled nonlinear optics (NLO) side chain polymers.A simple procedure to determine the rotational diffusion constant Dr is given and Dr values of several polymer systems have been evaluated and compared with each other.It appears that,starting from the conventional and well known poled polymer system currently applied,a further lowering of Dr by about 3 orders of magnitude is necessary in order to reach an acceptable orientational stability or lifetime of poled polymers for practical applications.Attempts have been made to introduce electron push-pull substituents into high thermostable molecular frameworks and results of preliminary measurements are reported. 相似文献
64.
Using the total human/mouse DNA as the probe, screening has been carried out three times with in situ plaque hybridization to obtain the single-copy DNA sequence from the human X chromosome genomic library. The effective rate of screening is 1. 45%. DNAs from clones containing single-copy inserts have been analyzed by a panel of hybrid cells with or without human X chromosome. Three segments, designated by DXFD52,73,75, are mapped to the X chromosome. DXFD52 has been precisely localized on Xq12-q13 with in situ chromosomal hybridization. DXFD52 has been partially sequenced. The results indicate that DXFD52 is a new isolated single-copy segment on the X chromosome. Great progress in the RFLPs study with DXFD52 has been achieved in the population of Chongqing, Sichuan Province. The results show that the DXFD52 can be used to detect the RFLP with Hind Ⅲ, Bgl Ⅱ, and Hinf Ⅰ. DXFD52 will be a potential "landmark" for the construction of the complete linkage map of human genome and the analysis of genomic s 相似文献
65.
LiMeiQIU FenLIU LiangZhongZHAO 《中国化学快报》2003,14(10):1058-1061
The effect of low energy electron (LEE) exposure on ISS, including on the sputter peak and scatter peak as well as on ion neutralization, has been investigated for different samples. Some new results are discussed. 相似文献
66.
A new triterpenoid saponin was isolated by bioactivity-guided isolation from "Gualou-xiebai-baijiu-tang" consisting ofFructus trichosanthisi and Bulbus allii macrostemi. Its structure was determined as 3-O-β-D-galactopyranosyl-hederagenin 28-O-β-D-xylopyranosyl (1→6)- β-D-galactopyranosyl ester by means of chemical evidences and spectral analysis. 相似文献
67.
Error of DIAL-measured Ozone Concentration and a Three-Wavelength Inversion Technique 总被引:1,自引:0,他引:1
邱金桓 《中国科学B辑(英文版)》1993,(11)
Sensitivity of the error in the stratospheric ozone concentration measured by DIAL to the scattering property of the stratospheric aerosol is studied through both theoretical analysis and numerical experiment in this paper, and based on the sensitivity, a three-wavelength lidar inversion technique is proposed for a simultaneous determination of ozone concentration profile, aerosol backscatter coefficient profile and its size distribution in the stratosphere. It is found from the sensitivity study that there is a considerable effect of the stratospheric aerosol on accuracy of the ozone concentration solution. If the aerosol scattering is neglected, a large error of the solution can be obtained, especially when there is the stratospheric volcanic cloud, the error can be up to 100%. According to numerical experiments, a great improvement of the ozone concentration solution is obtained by using the present three-wavelenght inversion method. 相似文献
68.
This paper reported the research results concerning the surface characterization ofpolystyrene-graft-w-stearyl poly(ethylene oxide) (PS-g-SPEO) by means of XPS,contactangle measurement and TEM, and its in vitro blood compatibility assessment by measuringthe plasma recalcification time (RT) and partial thromboplastin time (PTT). The XPSresults demonstrated that the surface and bulk composition of the PS-g-SPEO graftcopolymers differ remarkably from each other,and that SPEO component was constantlyenriched at the copolymer/air interface. Contact angle studies indicated that the surfacewater wettability can be adjusted effectively by changing the composition of the copolymer.PS-g-SPEO graft copolymers can undergo microphase separation as clearly illustrated byTEM photographs. The relationship between the surface properties of PS-g-SPEO graftcopolymer and its blood compatibility was also discussed. 相似文献
69.
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