内掺氮富勒烯N_2@C_(60)的几何结构和电子性质的密度泛函计算研究

采用密度泛函理论中的广义梯度近似对内掺氮富勒烯N2@C60的几何结构和电子性质进行计算研究.发现在N2@C60中,氮倾向以分子形式存在于C60中心处.键长分析、能级图、态密度图和电荷分析表明内掺氮分子对C60几何结构和电子结构带来的影响甚微.     

Ab initio study of phase stability,thermodynamic and elastic properties of C3N2 derived from cubic C20

In this work, we report a quite different conclusion from Tian et al. [Phys. Rev. B 78 (2008) 235431]. It is proved that β-C₃N₂ is the only phase under high pressure, and α-C₃N₂ does not exist. β-C₃N₂ is a covalent crystal composed of strong CC and CN covalent bonds. Band gap of β-C₃N₂ increases with pressure. The width of antibonding state, shown in partial density of states (PDOS), keeps about 5 eV with rising pressures, which brings stable CN or CC covalent bonds. At sufficiently low temperatures, heat capacity (C_v) is proportional to T³; and at intermediate temperatures, C_v is governed by the details of vibrations of the atoms; finally, C_v reaches to β-C₃N₂'s Dulong–Pettit limit (about 120 J/mol K). Though thermal expansion coefficient (α) increases with temperature, α is less than 1×10⁻⁵ K⁻¹. Elastic constants rise with pressure, but shear moduli is quite steady which increases just a little with pressures.     

g-C3N4负载双金属Rh@Ru催化氨硼烷析氢反应机理研究

本文采用密度泛函理论,研究了双金属Rh@Ru在g-C₃N₄上不同负载位点,确定了稳定的催化剂构型,并详细研究了该催化剂催化氨硼烷析氢的反应机理。通过比较氨硼烷析氢反应三条路径所需活化能,发现路径III控制步骤活化能较低,而路径I、II所需活化能较高,反应路径III更容易进行,I为最优析氢路径。从微观角度揭示双贵金属Rh@Ru负载g-C₃N₄催化氨硼烷析氢的三条机理,希望为氨硼烷析氢催化剂的优化和设计提供理论信息。     

Electronic spectroscopy of some isoelectronic MM′(CO)10 (M,M′ = Mn,Cr, Tc,Mo, Re,W) from time-dependent density functional theory

The electronic spectra of 12 isoelectronic binuclear decacarbonyls MM′(CO)₁₀ have been calculated, using time-dependent density functional theory (TD-DFT). The geometry has been optimised using the B3LYP functional. The energy of some well-known bands is calculated with the same functional for Mn₂(CO)₁₀ and other compounds as a test, using the same functional. The calculated values for the energy and the oscillator strength are in good fitting with experimental and reference data, and they show very small dependence on the basis. Then, the same calculation has been carried out for all the compounds up to 150 states. The strongest calculated transitions are summarised and assigned.     

Structure and stability of various states of the EuC and EuC2 molecules

B3LYP level density functional theory （DFT） and multiconfiguration self-consistent-field （MCSCF） level ab initio method calculations have been performed on the basis of relativistic effective core potentials to investigate the nature of EuC and EuC2 molecules. The computed results indicate that the ground states of EuC and EuC2 are ^12∑^＋ and SA2, respectively. Dissociation potential energy curves of the low-lying electronic states of EuC have been calculated using the MCSCF method, and the same level calculation on EuC2 indicates that the dissociation energy of EuC2 of ground state compares well with the available experimental data. The bond characteristic is also discussed using Mulliken populations.     

Sonocatalytic degradation of Rhodamine B in the presence of C60 and CdS coupled TiO2 particles

CdS-TiO₂ and CdS-C₆₀/TiO₂ were prepared using C₆₀, cadmium acetate dehydrate [(CH₃COO)₂Cd·2H₂O], sodium sulfide (Na₂S·5H₂O) and titanium (IV) n-butoxide by a sol-gel method. The prepared sonocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX) and transmission electron microscopy (TEM). A rhodamine B (RhB) solution under ultrasonic irradiation was used to determine the catalytic activity. Excellent catalytic degradation of an RhB solution was observed using the CdS-C₆₀/TiO₂ composites under ultrasonic irradiation. C₆₀ coupled CdS-TiO₂ can enhance the Brunauer-Emmett-Teller (BET) surface area and increase the decolorization rate for rhodamine B solution. The results also shows that increase the content of CdS can enhance the catalytic activity.     

内掺过渡金属非典型富勒烯M@C22(M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni) 几何结构、电子结构、稳定性和磁性的密度泛函研究

采用密度泛函理论中广义梯度近似对非典型富勒烯C₂₂和过渡金属内掺衍生物M@C₂₂(M=Sc,Ti,V,Cr,Mn,Fe,Co和Ni)的几何结构和电子结构进行计算研究.发现非典型富勒烯C₂₂的基态结构是含有一个四碳环的单重态笼状结构.过渡金属原子的掺入明显提高了体系的稳定性. C-M键既有一定共价性又有一定离子性.磁性、能级图、轨道分布和态密度图分析表明: M原子的3d轨道和碳笼的C原子的原子轨道之间存在较强的轨道杂化. Ti, Cr, Fe和Ni内掺的结构出现磁性完全猝灭现象. Sc和碳笼间是弱反铁磁作用, V,Mn和Co与碳笼间是弱铁磁作用.     

Effects of RE2O3 (RE = Tm, Sc, Yb) addition on the superconducting properties of ErBa2Cu3Oy

We investigated the effects of added Tm₂O₃, Sc₂O₃, and Yb₂O₃ on the superconducting properties of sintered Er123 samples. Tm₂O₃ addition caused the least T_c degradation, exhibiting a T_c above 90 K even for 17 vol% addition. Samples with added Sc₂O₃ maintained a T_c at above 90 K up to an addition of 7.2 vol%, while Yb₂O₃-containing samples showed a monotonic decrease in T_c with increased vol% of added Yb₂O₃. Tm₂O₃-containing samples exhibited a slight increase in J_c(0.1 T)/J_c(0) and had constant J_c values even for 17 vol% addition. XRD and SEM results indicate that the Tm₂O₃ is very stable in the superconducting matrix.     

Influence of deposition temperature on the structural and morphological properties of Be3N2 thin films grown by reactive laser ablation

Be₃N₂ thin films have been grown on Si(1 1 1) substrates using the pulsed laser deposition method at different substrate temperatures: room temperature (RT), 200 °C, 400 °C, 600 °C and 700 °C. Additionally, two samples were deposited at RT and were annealed after deposition in situ at 600 °C and 700 °C. In order to obtain the stoichiometry of the samples, they have been characterized in situ by X-ray photoelectron (XPS) and reflection electron energy loss spectroscopy (REELS). The influence of the substrate temperature on the morphological and structural properties of the films was investigated using scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD). The results show that all prepared films presented the Be₃N₂ stoichiometry. Formation of whiskers with diameters of 100-200 nm appears at the surface of the films prepared with a substrate temperature of 600 °C or 700 °C. However, the samples grown at RT and annealed at 600 °C or 700 °C do not show whiskers on the surface. The average root mean square (RMS) roughness and the average grain size of the samples grown with respect the substrate temperature is presented. The films grown with a substrate temperature between the room temperature to 400 °C, and the sample annealed in situ at 600 °C were amorphous; while the αBe₃N₂ phase was presented on the samples with a substrate temperature of 600 °C, 700 °C and that deposited with the substrate at RT and annealed in situ at 700 °C.     

Equilibrating of 15N-Gases by Electrodeless Discharge: A Method of Indirect Mass Spectrometric Analysis of 30N2 for Denitrification Studies in Soils

Abstract

The estimation of denitrification in soil by the ¹⁵N tracer technique includes isotope analysis of gas samples with a nonrandom distribution of the N₂ mole masses of 28, 29 and 30. In that case the emission of total ¹⁵N is underestimated by calculating ¹⁵N atom fractions from the ²⁹N₂/²⁸N₂ ratio if ³⁰N₂ is not considered. ³⁰N₂ can be measured indirectly in N₂ enriched with ¹⁵N with nonrandom distribution of mole masses by mass spectrometric analysis. The nitrogen fraction of gas samples was transferred to discharge tubes. Microwaves (60 sec) generated an electrodeless discharge of the gas which caused a temporary split-up of N₂ molecules and thus established an equilibrium distribution of the mole masses. The ²⁹N₂/²⁸N₂ ratio was measured in equilibrated and in untreated samples to calculate the real emission of ¹⁵N. The measurements of ¹⁵N standard gases by this method satisfactorily coincided with calculated values for ¹⁵N atom fraction above a concentration of 50 δ‰.     

Ion implantation effects in glasses

Abstract

Ion implantation can be used to introduce network damage and to alter the chemical composition in glasses. Structural changes can be inferred from IR measurements near 1000 cm^?1 and by optical absorption near 2150 Å. Implantation-induced damage decreases the implanted volume in fused silica with consequent changes in the refractive index, the near-surface hardness, and the tensile surface stress. Prior work in these areas is reviewed. Implantation into alkali silicate glasses depletes the alkali content in the implanted region. These changes allow preferential surface crystallization in Li₂O-2SiO₂ glasses. Crystallization of amorphous SiO2 can be induced by implantation of Li. Insight into the crystallization process is obtained by following the associated ion movement by elastic recoil detection (ERD) and optical techniques. Implantation of 20keV H shows that saturation of implanted H-sites in fused silica occurs at about 2.2 × 10²¹ H/cm³ in agreement with free volume estimates of the maximum number of available interstitial sites. Details of H and D interactions in fused silica were studied as a function of fluence and temperature. Results are of interest in studies of corrosion in glasses considered for nuclear waste encapsulation and for components in fusion reactors.

IV Summary     

The high pressure synthesis of the graphitic form of C3N4

Abstract

Basing on “ab-initio” calculations, C₃N₄ was claimed to be an ultra-hard material with a bulk-modulus close to that of diamond. Five different structural varieties were announced: the graphitic form, the zinc blende structure, the α and β forms of Si₃N₄ and another form, isostructural with the high pressure variety of Zn₂Si0₄.

Using the same strategy as that developed for diamond or c-BN synthesis, it appears that the graphitic form could be an appropriate precursor for preparing the 3D varieties. Two main problems characterize the C₃N₄ synthesis: (-) the temperature should be reduced in order to prevent nitrogen loss, (-) the reactivity of the precursors should be improved.

Consequently, we have developed a new process using the solvothermal decomposition of organic precursors containing carbon and nitrogen in the presence of a nitriding solvent. The resulting material, with a composition close to C₃N₄, has been characterized by different physico-chemical techniques.     

Roles of γ-Fe2O3 in fly ash for mercury removal: Results of density functional theory study

First-principle calculations based on density function theory (DFT) are used to clarify the roles of γ-Fe₂O₃ in fly ash for removing mercury from coal-fired flue gases. In this study, the structure of key surface of γ-Fe₂O₃ is modeled and spin-polarized periodic boundary conditions with the partial relaxation of atom positions are employed. Binding energies of Hg on γ-Fe₂O₃ (0 0 1) perfect and defective surfaces are calculated for different adsorption sites and the potential adsorption sites are predicted. Additionally, electronic structure is examined to better understand the binding mechanism. It is found that mercury is preferably adsorbed on the bridge site of γ-Fe₂O₃ (0 0 1) perfect surface, with binding energy of −54.3 kJ/mol. The much stronger binding occurs at oxygen vacancy surface with binding energy of −134.6 kJ/mol. The calculations also show that the formation of hybridized orbital between Hg and Fe atom of γ-Fe₂O₃ (0 0 1) is responsible for the relatively strong interaction of mercury with the solid surface, which suggests that the presently described processes are all noncatalytic in nature. However, this is a reflection more of mercury's amalgamation ability.