Superconductivity in Alkali-Doped C60

There ark three kinds of effective attractive interaction between C₆₀^2- and "nearly free" electron in A₃C₆₀: 1) the strong short-range attraction between the low energy unoccupied orbital of C₆₀^2- ions and the "nearly free" electrons; 2) the potential barrier due to large angular momentum of t_1u orbital; 3) the A⁺ crystal field forced "nearly free" electrons in C₆₀^2- neighborhood. All effective attraction coupling with the A⁺ optical modes and the vibration modes of C₆₀ mass center produces a strong electron-phonon interaction. It plays a principal role for A₃C₆₀ superconductivity. Based upon this mechanism critical temperature and other properties of superconductivity state can be explained by means of the BCS theory.     

富勒烯C20四聚体的结构与性能研究

采用密度泛函理论(DFT)中的杂化密度泛函(B3LYP)方法, 在6-31 G基组水平上对C₂₀四聚体进行了几何参数全优化, 得到了基态构型, 并对其稳定性、电子结构、极化率和芳香性进行了计算研究. 结果表明: C₂₀碳笼以[2+2]加成方式结合形成C₂₀四聚体, 具有良好的热力学稳定性; C原子内部以sp²的方式杂化, C原子之间有少量电荷转移; C₂₀ 四聚体的IR和Raman光谱都有较多的振动峰; 随碳笼数的增加, C₂₀聚合物中原子间的成键相互作用随之增强; C₂₀四聚体具有芳香性.     

(C_5H_(11)N_2)~+和(C_7H_(12)N_2)~(2+)的NMR研究

结合1H NMR,13C NMR谱,分别对钨、钼配合物{WO2(C10H6O2)2(C5H11N2)2[H2N(CH2)3NH2]}3(1),{(C5H11N2)2[H2N(CH2)3NH2][MoO2(C10H6O2)2]}(2),{(C7H12N2)2[MoO2(C10H8O2)2]}(3)晶体结构中小分子环进行了归属.其中,配合物1和2中(C5H11N2)+的NMR研究证实了六元环由1,3-丙二胺和乙腈化合而成,配合物3中(C7H12N2)2+的NMR谱图证实了七元环由乙二胺和乙酰丙酮化合而成,并且推导出这些亲核加成-消除反应的反应机理.配合物1~3中的小分子环的合成在其它体系中尚未见报导,而在合成它们的反应中作为新产物随主体晶体析出,并由晶体结构解析和NMR得到了证实.     

Theory,preparation, properties and catalysis application in 2D graphynes-based materials

Carbon has three hybridization forms of sp⁻, sp²⁻ and sp³⁻, and the combination of different forms can obtain different kinds of carbon allotropes, such as diamond, carbon nanotubes, fullerene, graphynes (GYs) and graphdiyne (GDY). Among them, the GDY molecule is a single-layer two-dimensional (2D) planar structure material with highly π-conjugation formed by sp⁻ and sp²⁻ hybridization. GDY has a carbon atom ring composed of benzene ring and acetylene, which makes GDY have a uniformly distributed pore structure. In addition, GDY planar material have some slight wrinkles, which makes GDY have better self-stability than other 2D planar materials. The excellent properties of GDY make it attract the attention of researchers. Therefore, GDY is widely used in chemical catalysis, electronics, communications, clean energy and composite materials. This paper summarizes the recent progress of GDY research, including structure, preparation, properties and application of GDY in the field of catalysts.     

添加Fe(C5H5)2合成氢掺杂金刚石大单晶及其表征

在Ni₇₀Mn₂₅Co₅-C体系中添加含氢化合物Fe(C₅H₅)₂作为新型氢源, 利用温度梯度法, 在压力为5.5-6.0 GPa、温度为1280-1400 ℃的条件下, 成功合成出氢掺杂的宝石级金刚石大单晶. 通过傅里叶显微红外光谱发现, 随着Fe(C₅H₅)₂添加量的增加, 合成晶体中与氢相关的对应于sp³杂化C-H键的对称伸缩振动和反对称伸缩振动的红外特征峰2850和2920 cm^-1逐渐增强, 而晶体中氮含量却逐渐减少. 通过合成晶体的拉曼光谱分析发现, 金刚石的拉曼峰伴随Fe(C₅H₅)₂的添加向高频偏移, 这表明氢的进入在金刚石内部产生了压应力. 观察扫描电子显微镜图像发现, 在低含量Fe(C₅H₅)₂添加时晶体表面平滑, 而高含量添加时晶体表面缺陷增多, 且呈现出气孔状. 使用新的添加剂Fe(C₅H₅)₂作为氢源, 合成出含氢宝石级金刚石单晶, 丰富了金刚石单晶中对氢的研究内容, 也可为理解天然金刚石的形成机理提供帮助.     

Pseudo-copper Ni–Zn alloy catalysts for carbon dioxide reduction to C2 products

Electrocatalytic CO₂ reduction reaction (CO2RR) to obtain C₂ products has drawn widespread attentions. Copper-based materials are the most reported catalysts for CO₂ reduction to C₂ products. Design of high-efficiency pseudo-copper catalysts according to the key characteristics of copper (Cu) is an important strategy to understand the reaction mechanism of C₂ products. In this work, density function theory (DFT) calculations are used to predict nickel–zinc (NiZn) alloy catalysts with the criteria similar structure and intermediate adsorption property to Cu catalyst. The calculated tops of 3d states of NiZn3(001) catalysts are the same as Cu(100), which is the key parameter affecting the adsorption of intermediate products. As a result, NiZn3(001) exhibits similar adsorption properties with Cu(100) on the crucial intermediates *CO₂, *CO and *H. Moreover, we further studied CO formation, CO hydrogenation and C–C coupling process on Ni–Zn alloys. The free energy profile of C₂ products formation shows that the energy barrier of C₂ products formation on NiZn3(001) is even lower than Cu(100). These results indicate that NiZn3 alloy as pseudo-copper catalyst can exhibit a higher catalytic activity and selectivity of C₂ products during CO₂RR. This work proposes a feasible pseudo-copper catalyst and provides guidance to design high-efficiency catalysts for CO₂RR to C₂ or multi-carbon products.     

High-order harmonic generation of the cyclo[18]carbon molecule irradiated by circularly polarized laser pulse

High-order harmonic generation of the cyclo[18]carbon (C₁₈) molecule under few-cycle circularly polarized laser pulse is studied by time-dependent density functional theory. Compared with the harmonic emission of the ring molecule C₆ H₆ having similar ionization potential, the C₁₈ molecule has higher efficiency and cutoff energy than C₆ H₆ with the same laser field parameters. Further researches indicate that the harmonic efficiency and cutoff energy of the C₁₈ molecule increase gradually with the increase of the laser intensity of the driving laser or decrease of the wavelength, both are larger than those of the C₆ H₆ molecule. Through the analysis of the time-dependent evolution of the electronic wave packets, it is also found that the higher efficiency of harmonic generation can be attributed to the larger spatial scale of the C₁₈ molecule, which leads to a greater chance for the ionized electrons from one atom to recombine with others of the parent molecule. Selecting the suitable driving laser pulse, it is demonstrated that high-order harmonic generation in the C₁₈ molecule has a wide range of applications in producing circularly polarized isolated attosecond pulse.     

Li2C2中电声耦合及超导电性的第一性原理计算研究

通过第一性原理密度泛函和超导Eliashberg理论计算, 我们研究了Li₂C₂在Cmcm相的电子结构和电声耦合特性, 预言这种材料在常压和5GPa下是由电声耦合导致的转变温度分别为13.2 K 和9.8 K的超导体, 为实验上探索包含一维碳原子链的材料中是否可能存在超导电性、发现新的超导体提供了理论依据. 如果理论所预言的Li₂C₂超导电性得到实验的证实, 这将是锂碳化物中转变温度最高的超导体, 高于实验观测到的LiC₂的1.9 K和理论预言的单层LiC₆的8.1 K超导转变温度.     

光谱参数法快速识别石油烃污染场地水体特征

水体受石油污染日趋广泛,给人类及生态环境带来严重威胁。快速、准确和可靠地监测水体石油污染状况,对于理解其环境行为和评估人体暴露风险至关重要。石油类组分往往具备较好的光谱响应,然而基于光谱技术快速监测实际石油烃污染水体却鲜有报道。该研究以典型石油污染场地的地下水和地表水为对象,在全面分析水质电导率、总有机碳,Cl-,NO-₃,SO2-₄,Na+,K+,Mg2+,Ca2+,NH+₄,挥发性有机物和石油烃C₆-C₉,C₁₀-C₁₄,C₁₅-C₂₈,C₂₉-C₄₀浓度基础上,对水体样品进行紫外-可见光光谱、同步荧光光谱、三维荧光光谱表征,采用多元数据分析手段评估光谱技术在石油污染场地快速识别应用的可能性。结果表明：①紫外-可见光光谱和同步荧光光谱参数表明,污染的地下水中含有大量芳香族化合物,且有机物分子结构复杂,含有大量的羟基、羰基、羧基和酯类等取代基,三维荧光光谱参数表明污染水体中有机物经过了长时间的生物转化,说明污染地下水中有机物稳定性强,降解性差;②三维荧光光谱图表现出Ⅰ和Ⅳ区明显的荧光峰,Ⅴ区存在肩峰的水体主要是苯系物污染,而三维荧光光谱图表现出Ⅱ和Ⅳ区明显的荧光峰,Ⅰ区存在肩峰的水体主要是萘系物污染,三维荧光光谱图表现出Ⅱ区最高荧光峰,Ⅰ,Ⅲ,Ⅳ和Ⅴ都存在肩峰的水体主要是萘系物和菲系物污染;③石油烃C₆-C₉组分浓度可采用紫外-可见光光谱参数S_308～363,SUVA₂₅₄和三维荧光光谱中Ⅰ区体积快速指示,石油烃C₁₀-C₁₄组分和总石油烃（TPH）浓度可采用三维荧光光谱中Ⅳ区体积快速指示,石油烃C₁₅-C₂₈和C₂₉-C₄₀组分浓度可采用三维荧光光谱中Ⅰ区体积快速指示。研究证实利用光谱参数结合多元数据分析可对石油污染水体进行快速识别,为地下水石油污染监测和修复提供了一种全新的快速在线监测分析方法。     

First-principles Study on the Magnetic,Half-metal and Thermoelectric Transport Properties of Inorganic-Organic Hybrid Compounds [C4N2H12][Fe4Ⅲ(HPO3)2(C2O4)3]

The electronic structure, magnetic and half-metal properties of inorganic-organic hybrid compound [C₄N₂H₁₂][Fe₄^Ⅲ(HPO₃)₂(C₂O₄)₃] are investigated by using the full-potential linearized augmented plane wave (FPLAPW) method within density-functional theory (DFT) calculations. The density of states (DOS), the total energy of the cell and the spontaneous magnetic moment of [C₄N₂H₁₂][Fe₄^Ⅱ(HPO₃)₂(C₂O₄)₃] are calculated. The calculation results reveal that the low-temperature phase of [C₄N₂H₁₂][Fe₄^Ⅲ(HPO₃)₂(C₂O₄)₃] exhibits a stable ferromagnetic (FM) ground state, and we find that this organic compound is a half-metal in FM state. In addition, we have calculated antiferromagnetically coupled interactions, revealing the existence of antiferromagnetic (AFM), which is in agreement with the experiment. We have also found that [C₄N₂H₁₂][Fe₄^Ⅲ(HPO₃)₂(C₂O₄)₃] is a semiconductor in the AFM state with a band gap of about 0.40 eV. Subsequently, the transport properties for potential thermoelectric applications have been studied in detail based on the Boltzmann transport theory.     

大气压甲烷针-板放电等离子体中粒子密度和反应路径的数值模拟

甲烷针-板放电与重油加氢耦合形成甲烷转化重油加氢,可实现重油高效加氢并增产高附加值低碳烯烃,有实践应用前景和科学研究意义.建立二维流体模型,对大气压甲烷针-板放电等离子体进行数值模拟,得到电场强度、电子温度和粒子密度的空间与轴向分布,总结反应产额并提炼生成各种带电和中性粒子的关键路径.模拟结果表明,CH_3~+和CH_4~+密度与电场强度和电子温度的轴向演化接近且密切相关;CH_5~+和C_2H_5~+密度沿轴向先增大后减小;CH_3与H密度的空间和轴向分布几乎相同;CH_2,C_2H_4与C_2H_5的粒子密度分布在靠近阴极的区域内明显不同而在正柱区内较为相像;电子与CH_4发生电子碰撞电离生成的CH_3~+和CH_4~+,CH_3~+和CH_4~+分别与CH_4发生分子碰撞解离生成C_2H_5~+和CH_5~+;电子与CH_4间的电子碰撞分解是生成CH_3,CH_2,CH和H的主导反应;CH_2与CH_4和电子与C_2H_4发生的反应分别是生成C_2H_4和C_2H_2的关键路径;电子与CH_4间的电子碰撞分解反应和CH_2与CH_4发生的反应的产额各占H_2总产额的52.15%和47.85%.     

Structural transitions of SWNT filled with C_(60) under high pressure

Raman spectra of C_(60) filled single-walled carbon nanotubes(C_(60)@SWNTs) with diameters of 1.3–1.5 nm have been studied under high pressure. A plateau in the pressure dependence of the G-band frequency at around 10 GPa was observed in both experiments with 514 nm and 830 nm excitation lasers, which is similar to the high pressure behaviors of pristine SWNTs. This structural transition has been assigned to the transformation into a peanut-like structure of the nanotubes. At pressure below 2 GPa, no obvious Raman signature related to the structural transition of nanotubes was observed, unlike what has been reported for C_(70) filled nanotubes. We discussed this point in terms of the arrangement differences of C_(60) and C_(70)molecules inside the nanotubes. At higher pressure up to 15 GPa, a graphite-like pressure evolution was observed in our C_(60)@SWNTs.     

Essence of Pseudogap and Oscillation in High-Temperature Cuprate Superconductor Junction of Pseudogap State

This paper gives methods to calculate the pairing temperature T*,at which a pseudogap is opened,and the superconducting temperature Tc,at which superconductivity appears,in the high-Tc cuprates,and demonstrates directly that at Tc ＜ T ＜ T* the pseudogap is the gap of Cooper pair without long-range phase coherence,and at T ＜ Tc there is long-range phase coherence between Cooper pairs.Based on the above clear physical picture on the pseudogap state and our mechanism for the ac Josephson effect,this paper proposes that there should be a novel oscillatory current in P-I-P junction,induced by a constant bias on the junction.Here,P represents the high-Tc curates in the pseudogap state,where Cooper pairs do not have long-range phase coherence,and I represents the thin insulating barrier.This paper conjectures that there is a possible high-temperature superconductivity in the heavily underdoped high-Tc cuprates.     

The interaction of C2Cl4 with fe(110)

Quantitative adsorption studies, temperature programmed desorption (TPD) and Auger spectroscopy have been used to study the interaction of C₂Cl₄ with Fe(110) at 90 and 325 K. At 90 K, multilayer C₂Cl₄ adsorption occurs. The following desorption products are observed in the temperature range of 90–1050 K: C₂Cl₄ from the multilayer and the monolayer, FeCl₂, and a high mass iron chloride species with mass spectrometer cracking products FeCl⁺₂, FeCl⁺, and Fe⁺. Irreversible dissociative C₂Cl₄ adsorption occurs at 325 K and the only desorption product which is observed is the high mass iron chloride species. Auger spectroscopy shows that surface carbon from C₂Cl₄ starts to diffuse into the bulk of the crystal at ˜ 480 K while small coverages of chlorine remain on the surface of the crystal even after heating to 1050 K. Comparison of the behavior of C₂Cl₄ and CCl₄ on Fe(110) indicates that radical products (·CCl₃ and :CCl₂) observed to be produced from CCl₄ adsorption are not produced from C₂Cl₄ adsorption. This difference is probably due to the enhanced surface reactivity of the C=C bond in C₂Cl₄. A special reactivity of iron defect sites for C₂Cl₄ is observed through the production of associated FeCl₂ species which desorb via zero-order kinetics with an activation energy of 44.8 ± 8.5 kcal/mol, the sublimation enthalpy of FeCl₂.     

偏硼酸钡低温相的晶体结构

本文报道了新型信频材料——偏硼酸钡[Ba₃(B₃O₆)₂]低温相的晶体结构。晶体属三方晶系,空间群为C₃⁴-R3,取六方坐标系,晶胞参数为a=b=12.532?,c=12.717?,z=6。在PhilipsPW-1100四圆衍射仪上收集到独立衍射693个。采用重原子法通过三维帕特逊和三维傅里叶合成测定结构,并用对角矩阵最小二乘法修正至R=0.046。该晶体是一个由Ba²⁺和(B₃O₆)^3-环交错组成的层状阶梯式结构。其阴离子(B₃O₆)^3-环基本上是平面状的。基团平面垂直于三次轴;Ba²⁺近邻有7个氧原子。将此结构与偏硼酸钡高温相比较表明,由于钡阳离子的非中心对称分布改变了阴离子硼氧环共轭基团的电子云密度,这一结构上的变化对该晶体的倍频效应做了主要贡献。 关键词：     

CHClF2在强红外激光作用下C2*d3Пg态的形成机制

用TEACO₂激光辐照CHCIF₂分子生成电子激发态C₂^*自由基,观察到斯旺带系的六个谱带。本文根据C₂分子态位能曲线的特点,提出C₂^*d³Π_g态的形成机制。C₂是少数较特殊的分子之一,其激发态b³Σ_g^-与第一激发态a关键词：     

表面吸附K原子的多层FeSe/SrTiO3(001)薄膜的抗磁响应的原位测量

SrTiO₃（001）单晶表面上生长的单层FeSe薄膜显示出了超乎寻常的高温超导电性,其超导增强机制的一个重要因素是电子由衬底转移到了单层FeSe薄膜当中.基于此认识,研究者们在吸附了钾（K）原子的多层FeSe薄膜表面上观察到了类似超导能隙的隧穿能谱和光电子能谱.但这种自上而下的电子掺入方式在多层FeSe薄膜表面上可能引起的高温超导电性,还缺乏零电阻或迈斯纳效应等物性测量实验的直接证实.本研究利用自行研制的一台特殊的多功能扫描隧道显微镜,在生长于SrTiO₃（001）衬底上的多层FeSe薄膜表面上,不但观察到了超导能隙随K吸附量的变化,而且利用原位双线圈互感测量技术,成功地的观察到了该薄膜的抗磁响应,并由此确定了该薄膜样品呈现迈斯纳效应的超导转变温度为23.9 K.其穿透深度随温度的变化呈二次幂指数关系,表明该体系的超导序参量很可能具有S^±配对对称性.     

ELECTRONIC STRUCTURE STUDIES OF THE C60 FILM CONDENSED ON 2H-MoS2(0001) SURFACE

The electronic structure and vibrational spectrum of the C₆₀ film condensed on a 2H- MoS₂(0001) surface have been investigated by X-ray photoelectron spectroscopy (XPS), ul-traviolet photoelectron spectroscopy (UPS), Auger electron spectroscopy (AES) and infrared high-resolution electron-energy-loss spectroscopy (HREELS). AES analysis showed that at low energy side of the main transition, C₆₀ contains a total of three peaks just like that of graphite. However, the energy position of the KLL main Auger transition of C₆₀ looks like that of diamond, indicating that the hybridization of the carbon atoms in C₆₀ is not strictly in sp²- bonded state but that the curvature of the molecular surface introduces some sp²pz- bonded character into the molecular orbitals. XPS showed that the C 1s binding energy in C₆₀ was 285.0eV, and its main line was very symmetric and offered no indication of more than a single carbon species. In UPS measurement the valence band spectrum of C₆₀ within 10eV below the Fermi level (E_F) shows a very distinct five-band structure that character-izes the electronic structure of the C₆₀ molecule. HREEL results showed that the spectrum obtained from the C₆₀ film has very rich vibrational structure. At least, four distinct main loss peaks can be identified below 200 meV. The most intense loss was recorded at 66 meV, and relatively less intense losses were recorded at 95, 164 and 197meV at a primary energy of electron beam E_P = 2.0eV. The other energy-loss peaks at 46, 136, 157 and 186meV in HREEL spectrum are rather weak. These results have been compared to infrared spectrum data of the crystalline solid C₆₀ taken from recent literatures.     

KCdF3晶体中Cr3+-Li+中心局域结构研究

利用零场分裂参量与晶体结构之间的定量关系,研究了双掺杂晶体KCdF₃:Cr³⁺,Li⁺的局域结构。指出,对于KCdF₃:Cr³⁺,Li⁺晶体,四角晶场的形成包含两个方面:(1)由于电荷补偿而产生的等效电荷形成的四角对称晶场;(2)Cr³⁺的局域结构发生晶格畸变而产生的四角对称晶场。事实上,当Cr³⁺和Li⁺掺入KCdF₃晶体时,Cr³⁺代替了Cd²⁺离子;由于Cr³⁺离子与Cd²⁺离子的半径不同、电荷不同、质量不同,导致Cr³⁺的局域结构发生晶格畸变,由此而产生四角对称晶场;由于电荷补偿,Li⁺离子取代了[001]方向与Cr³⁺离子邻近的Cd²⁺离子,由此产生的等效电荷而形成的四角晶场。这样,Cr³⁺的局域结构由O_h对称变为C_4v点对称。文中建立了ZFS参量和晶体结构之间的定量关系。在考虑晶格畸变和等效电荷的基础上,研究了KCdF₃:Cr³⁺,Li⁺晶体的ZFS参量,理论结果和实验符合很好。得到了F^-离子向中心离子分别移动为ΔR₁=0.00268nm,ΔR₂=0.001nm,ΔR₃=0.00165nm。     

N2在页岩干酪根上的吸附特征

采用密度泛函理论的wB97XD方法、RDG函数方法和counterpoise correction理论,研究氮气在干酪根C₂₈H₁₄O和氮掺杂干酪根C₂₇H₁₄ON上的吸附特征。结果表明：N₂在干酪根上的活性吸附位点为苯环上方中心位置,吸附能在8~10 kJ·mol^-1之间,N₂和干酪根之间的相互作用主要是范德华相互作用和空间排斥作用。氮掺杂改变了干酪根的构型和电子云分布,导致含氮杂环不再是稳定的活性吸附位点,增强了排斥作用,使吸附能略有减小。研究结果对理解干酪根吸附小分子的特征有重要意义,能够为页岩气的开采提供理论支持。