The density functional study of the stabilities,bond characters,static linear polarisabilities,and aromaticities of the ’in-out’ isomerism Hn-60@CnH60（n=70,72,74）

This paper uses the density functional theory to analyse the stabilities,bond characters,static linear polarisabilities,and aromaticities of the ’in-out’ isomerism H n-60 @C n H 60 (n=70,72,74).The binding energies,C-H bond energies,and energy gaps explore that the ’in-out’ isometric perhydrogenation of C n (n=70,72,74) can remarkably improve the stabilities.The static linear polarisabilies of H n-60 @C n H 60 (n=70,72,74) are indeed relative to their shapes,while they show almost nonaromatic character.This study can suggest that the ’in-out’ isometric perhydrogenation of fullerenes could lead to the invention of entirely novel potential hydrogen storage nanomaterials.     

WnNim(n+m=8)团簇的极性和光谱性质的理论研究

采用密度泛函理论(DFT)中的B3LYP方法,在LANL2DZ基组水平上对WnNim(n+m=8)团簇的各种可能构型进行了几何参数全优化,得到了它们的基态构型;并对基态构型的偶极距、极化率、红外光谱和拉曼光谱性质进行了分析,结果表明:团簇WnNim(n+m=8)都具有极性,富W团簇非线性光学效应强,容易被外加场极化;振动频率主要分布在0-350 cm-1范围内,团簇W4Ni4因其振动方式的特殊性,红外光谱和拉曼光谱在频率421.971 cm-1处,都有明显强峰;团簇W5Ni3因其结构的高对称性在振动光谱中出现多处共振现象.     

Scanning tunneling microscopy/spectroscopy on multi-layered cuprate superconductor Ba2Ca5Cu6O12 (O1−x Fx)2

Scanning tunneling microscopy/spectroscopy (STM/STS) measurements on multi-layered cuprate superconductor Ba₂Ca₅Cu₆O₁₂ (O_1−x F_x)₂ are carried out. STM topographies show randomly distributed bright spot structures with a typical spot size of 0.8 nm. These bright spots are occupied about 28% per one unit cell of c-plane, which is comparable to the regular amount of apical oxygen of 20% obtained from element analysis. Tunneling spectra simultaneously show both the small and the large gap structures. These gap sizes at 4.9 K are about Δ 15 meV and 90 meV, respectively. The small gap structure disappears at the temperature close to T_C, while the large gap persists up to 200 K. Therefore, these features correspond to the superconducting gap and pseudogap, respectively. These facts give evidence for some ordered state with large energy scale even in the superconducting state. For the superconducting gap, the ratio of 2Δ/K_BT_C = 4.9 is obtained with T_C = 70 K, which is determined from temperature dependence of the tunneling spectra.     

Effects of Fe2+ substitution on magnetic and dielectric properties of CdCr2S4

The magnetic and dielectric properties of polycrystalline Cd_{1 - x}Fe_xCr₂S₄ (0 ≤ x ≤ 0.9) are investigated. Upon substitution of Cd by Fe, the Curie temperature (T_C) is increased while the saturation magnetization is decreased. A low doping level of Fe increases the permittivity, while a high doping level decreases the permittivity, which is explained by the internal barrier layer capacitor model. Kinks are observed in the temperature-dependent permittivity and loss tangent near T_C for the samples with x= 0.5, 0.7, 0.9, implying the existence of the magnetodielectric effect. Furthermore, with the increase of Fe content, a decrease of anomaly deviation rate induced by internal molecular field is revealed in the permittivity, while an increase is observed for the loss tangent.     

Determination of optical nonlinearities in Cu(mpo)2 by Z-scan technique

The optical nonlinearities of Cu(mpo)₂ [formula = C₁₀H₈N₂CuO₂S₂] complex have firstly been investigated by using the Z-scan technique with a nanosecond-pulsed Nd:YAG laser at its second harmonic (532 nm) radiation. The nonlinear optical absorption and refraction coefficients of Cu(mpo)₂ have been measured with the different on-axial peak irradiances I ₀ at the waist ranging from 0.48 to 5.66 GW/cm². The nonlinear transmittance characteristics exhibit the near resonant two-photon absorption (TPA) at 532 nm and are explained by a population redistribution model. The nonlinear absorption originates from the near resonant TPA while the mechanism of the nonlinear refraction is the near resonant TPA transition enhancement. The linear increasing dependences of the optical nonlinearities on the incident irradiance arise from the population redistribution due to the near resonant TPA.     

Ab initio investigations of the charge transport properties of endohedral M@C20（M=Na and K）metallofullerenes

Using density functional theory and quantum transport calculations based on nonequilibum Green’s function formalism,we investigate the charge transport properties of endohedral M@C 20 (M=Na and K) metallofullerenes.Our results show that the conductance of C 20 fullerene can be obviously improved by insertion of alkali atom at its centre.Both linear and nonlinear sections are found on the I-V curves of the Au-M@C 20-Au two-probe systems.The novel negative differential resistance behaviour is also observed in Na@C 20 molecule but not in K@C 20.     

Quasi-two-dimensional magnetism in (CnH2n+1NH3)2CuCl4 studied by electron paramagnetic resonance

The quasi-two-dimensional magnetism in the layered transition metal compound (C_nH_2n+1NH₃)₂CuCl₄ (n=10, 14) was investigated by means of electron paramagnetic resonance (EPR) and superconducting quantum interference device measurements. As a result, the high temperature magnetic phase transitions were reflected in the EPR parameters in a sensitive manner.     

Dynamic holograms recording in fullerene-containing solid-state matrices: Porous glass slides and PMMA films

Fullerene-containing solid-state matrices were studied theoretically and experimentally as the active material for all-optical switching devices. Dynamics hologram recording and spectral analysis were used to study temporal stability and efficiency of nonlinear response of the media. Porous glass and polymethylmethacrylate hosts were utilized as C₆₀-containing matrices. Experiments were carried out using nano- and picosecond laser radiation with wavelength 532 nm.     

Photoemission intensity oscillations in the valence bands of C70 film

We have measured and analyzed the photoemission spectra (PES) of a C₇₀ film in the photon energy region from 13.4 eV to 98.4 eV. The photoelectron intensities of two C 2p π-derived features (denoted by A and B) oscillate regularly in the whole energy region with some fine structures below ∼30 eV. To obtain the detailed information of the oscillations, we have developed a sophisticated but practical procedure for intensity calculation. The procedure consists of two core concepts. The first is ascribing the PES features to their corresponding molecular orbitals with the help of density functional calculations. The second is a background subtraction algorithm. With this procedure, we obtained the oscillating behavior for individual features (A and B), which is by and large consistent with the predictions based on the spherical symmetric approximation although C₇₀ has the ellipsoidal shape. Owing to the solid state effect, the oscillating amplitudes of the A/B intensity ratios are smaller than those of gas phase C₇₀, but an orbital shift reported recently was not observed on our sample. The oscillating curve of a deeper feature, which consists of both σ and π states, are also reported.     

Co(S1-xSex)2系统中的铁磁量子相变

针对Co(S_1-xSe_x)₂系统在x=0.11附近发生的铁磁金属到顺磁金属相变,制备了一系列不同Se替代浓度的多晶样品.通过对其结构和电阻率-温度ρ(T)关系的系统观测,结果发现,样品铁磁相变温度T_C随着Se替代浓度x值的增加,以(1-x)^1/2关系单调下降,其二级铁磁相变转变为一级相变 关键词： 量子相变 自旋量子涨落 1-xSe_x)₂')" href="#">Co(S_1-xSe_x)₂     

Investigation of optical nonlinearities in Pd(po)2 by Z-scan technique

With nanosecond scale at a 532 nm wavelength, we firstly measured the nonlinear optical absorption and refraction coefficients of Pd(po)₂ complex by using Z-scan technique, here Hpo=1-hydioxy-2-pyridone. We describe an empirical expression for the case when nonlinear refraction is accompanied by nonlinear absorption to separately evaluate the nonlinear refraction and the nonlinear absorption by performing straightforward measurements with the aperture removed. The nonlinear optical response of Pd(po)₂ was determined by the linear decreasing irradiance-dependence. The nonlinear absorption originates from the near resonant two-photon absorption while the mechanism of the nonlinear refraction is the near resonant two-photon absorption transition enhancement. The linear increasing dependences of the optical nonlinearities on the incident irradiance arise from the population redistribution due to the near resonant two-photon absorption.     

Pr0.7(Sr1-xCax)0.3MnO3多晶体系中的小极化子性质

采用基于柠檬酸体系的溶胶-凝胶法制备了Pr_0.7（Sr_1-xCa_x）_0.3MnO₃系列的多晶块材, 同时还用脉冲激光沉积技术（PLD）在SrTiO₃（100）衬底上外延生长了同一系列的薄膜, 系统研究了它们的晶格结构和电输运行为. 多晶和薄膜样品都具有正交晶格结构, 电输运行为在居里温度T_Ｃ以上的高温顺磁相都很好 关键词： 0.7（Sr_1-xCa_x）_0.3MnO₃')" href="#">Pr_0.7（Sr_1-xCa_x）_0.3MnO₃ 绝热小极化子模型 双交换作用 Jahn-Teller晶格畸变     

Rb掺杂C60单晶的相衍变和电子态

在C₆₀单晶超高真空解理面上制备C₆₀的Rb填隙化合物薄膜.用同步辐射光电子能谱研究了相衍变过程.观察到对应于固溶相、Rb₁C₆₀和Rb₃C₆₀的电子态密度分布.当数纳米厚Rb₃C₆₀薄膜在C₆₀单晶（111）解理面形成后，室温条件下进一步沉积Rb至样品表面不产生fcc到bct或bcc结构相变.C_{60 关键词： 4}C₆₀和Rb₅C₆₀吸附相')" href="#">金属性Rb₄C₆₀和Rb₅C₆₀吸附相 60单晶')" href="#">C₆₀单晶 相衍变 同步辐射光电子能谱     

富勒烯衍生物苯基C71-丁酸甲酯的结构和电学性质第一性原理研究

使用B3LYP/6-31G（d）方法对有机太阳电池中作为电子受体材料的富勒烯衍生物苯基C₇₁-丁酸甲酯（［70］PCBM）的同分异构体进行了计算.PCBM与C₇₀通过六元环和六元环共用的CC双键加成得到的产物是热力学控制产物;通过五元环和六元环共用的C—C键加成得到的产物则是动力学控制产物.［70］PCBM与C₇₀的第一绝热电子亲和势很接近.PCBM对前线轨道贡献很小,［70］PCBM的最高占据分子轨道和最低未占据分子轨道（LUMO）的电子云主要分布在C₇₀笼上.PCBM提升了C₇₀的LUMO能级水平,有利于提高太阳电池的光电转换效率.自然布居分析表明,PCBM与C₇₀之间没有发生显著的电荷转移.所有的性质研究表明,PCBM基团并不涉及电池光电转换过程,但在调整C₇₀能级水平提高光电转换效率中发挥了重要作用. 关键词： 71-丁酸甲酯')" href="#">苯基C₇₁-丁酸甲酯 电子受体 结合能 第一绝热电子亲和势     

Exploring the mechanism of NO–C2H4 reactions on the surface of stepped Pt(3 3 2)

Fourier transform infra red reflection–absorption spectroscopy (FTIR-RAS), thermal desorption spectroscopy (TDS), and auger electron spectroscopy (AES), were employed to explore the mechanism of NO reduction in the presence of C₂H₄ on the surface of stepped Pt(3 3 2). Both NO–Pt and C₂H₄–Pt interactions are enhanced when NO and C₂H₄ are co-adsorbed on Pt(3 3 2). As a result, C₂H₄ is dissociated at surface temperatures as low as 150 K, and the N–O stretch band is weakened. The presence of post-exposed C₂H₄ leads NO desorption from steps to decrease significantly, but the same effect on NO desorption from terraces becomes appreciable only at higher post-exposures of C₂H₄, e.g., 0.6 L and 1.2 L, and proceeds to a much slighter extent. Auger spectra indicate that as a result of the reaction with O from NO dissociation, the amount of surface C species is greatly reduced when NO is post-exposed to a C₂H₄ adlayer. It is concluded that reduction of NO in the presence of C₂H₄ proceeds very effectively on the surface of the Pt(3 3 2), through a mechanism of NO dissociation and subsequent O removal. Following this mechanism, the significant dissociation of adsorbed NO molecules on steps at surface temperatures below 400 K, and subsequent rapid reaction between the resultant O and C-related species, accounts for the considerable amount of N₂ desorption at temperatures below 400 K.     

Flame structure studies of rich ethylene-oxygen-argon mixtures doped with CO2, or with NH3, or with H2O

Structures of several premixed ethylene-oxygen-argon rich flat flames burning at 50 mbar have been established by using molecular beam mass spectrometry in order to investigate the effect of CO₂, or NH₃, or H₂O addition on species concentration profiles. The aim of this study is to examine the eventual changes of profiles of detected hydrocarbon intermediates which could be considered as soot precursors (C₂H₂, C₄H₂, C₅H₄, C₅H₆, C₆H₂, C₆H₄, C₆H₆, C₇H₈, C₆H₆O, C₈H₆, C₈H₈, C₉H₈ and C₁₀H₈). The comparative study has been achieved on four flames with an equivalence ratio (f) of 2.50: one without any additive (F2.50), one with 15% of CO₂ replacing the same quantity of argon (F2.50C), one with 3.3% of NH₃ in partial replacement of argon (F2.50N) and one with 13% of H₂O in replacement of the same quantity of argon (F2.50H). The four flat flames have similar final flame temperatures (1800 K).CO₂, or NH₃, or H₂O addition to the fresh gas inlet causes a shift downstream of the flame front and thus flame inhibition. Endothermic processes CO₂ + H = CO + OH and H₂O + H = H₂ + OH are responsible of the reduction of the hydrocarbon intermediates in the CO₂ and H₂O added flames through the supplementary formation of hydroxyl radicals. It has been demonstrated that such processes begin to play at the end of the flame front and becomes more efficient in the burnt gases region.The replacement of some Ar by NH₃ is responsible only for a slight decrease of the maximum mole fraction of C₂H₂, but NH₃ becomes much more efficient for C₄H₂ and C₅ to C₁₀ species. Moreover, the efficiency of NH₃ as a reducing agent of C₅ to C₁₀ intermediates is larger than that of CO₂ and H₂O for equal quantities added.     

电子型掺杂高温超导体La2-xCexCuO4飞秒时间分辨动力学研究

利用飞秒时间分辨光抽运探测技术研究了电子型掺杂La_2-xCe_xCuO₄(LCCO)高温超导材料的准粒子超快动力学过程.得到低温(T<0.7T_c)、转变温度附近(0.7T_c≤T≤T_c)和高温(T>T_c)三个温区内的动力学行为.研究发 关键词： 电子型掺杂高温超导体 飞秒时间分辨 准粒子 声子瓶颈     

New FIR laser lines from optically pumped C2H3F, C2H3Cl, C2H3Br, C2H3CN, C2H5F, CH2CF2, HCOOH and CH3Br

Twenty-seven new cw far infrared laser lines with wavelengths between 137 and 988m have been observed from optically pumping C₂H₃F, C₂H₃Cl, C₂H₃Br, C₂H₅F, C₂H₃CN, CH₂CF₂, HCOOH and CH₃Br with a CO₂ laser. The wavelengths of these FIR laser lines were determined together with their optimum pressures and relative intensities.     

异质富勒烯C19M(M=Cr,Mo,W)的结构和电子性质的计算研究

采用密度泛函理论(DFT)中的B3LYP方法, 在LANL2DZ基组水平上, 优化了C₁₉M(M=Cr,Mo,W)团簇的几何结构, 得出了它们的基态构型, 并研究了基态结构的物理化学性能.结果表明: 不同的M原子替换后, C₁₉M的动力学稳定性相差不大, 而热力学稳定性随着M原子序数的增加而逐渐升高; 通过对C₁₉M的前线轨道分析发现, M原子对各个轨道均有一定的贡献, M原子对各个轨道的贡献大致随着M原子序数的增加而增加, C₁₉M中金属原子M(M=Cr,Mo,W)上集中了大量的正电荷; C₁₉M的芳香性随着M原子序数的增加而减弱.     

Al2O3X(X=H,D, T)的电子振动近似理论方法研究

用密度泛函理论(DFT)方法在6-311++G(d,p)水平上对Al₂O₃X(X=H, D, T)分子较低能量的几何构型进行了优化. 计算结果表明该分子有两个可能基态, 即Al₂O₃X(X=H,D,T)(²A′)C_s和Al₂O₃X 关键词： 2O₃X(X=H;D;T)分子团簇')" href="#">Al₂O₃X(X=H;D;T)分子团簇 热力学函数 氢同位素效应 吉布斯自由能改变