掺杂Fe对VH2解氢性能影响的第一性原理研究

采用密度泛函理论(DFT)的第一性原理的平面波超软赝势方法,研究了Fe掺杂对VH₂的电子结构和解氢性能的影响.通过计算Fe掺杂VH₂前后体系的合金形成热、V-H之间的重叠布居数、电子态密度、电子密度,发现Fe掺杂VH₂后,随着Fe含量增加,合金体系的晶胞参数和晶胞体积逐渐减少;体系的负合金形成热逐渐减少,且掺杂后体系的负合金形成热都比VH₂的负合金形成热小,体系的稳定性降低;电子态密度计算也显示Fe掺杂后费米能级处的电子浓度增加,体系稳定性降低;重叠布居数和电子密度计算表明掺杂后V-H之间的重叠布居数由0.1减小为0.08或0.09,V-H之间的电子密度减少,说明V和H原子之间的相互作用减弱,提高了VH₂的解氢性能.计算结果解释了实验现象. 关键词： Fe掺杂 电子结构 解氢性能 第一性原理计算     

SiN掺杂提高BaMgAl10O17:Eu2+荧光粉光学性能的第一性原理研究

使用基于密度泛函理论的CASTEP软件计算了BAM:Eu²⁺(BaMgAl₁₀O₁₇:Eu²⁺)荧光粉在SiN掺杂前后的能带、态密度、吸收光谱和Mulliken布居．Eu²⁺处于BR位置光吸收更强;SiN掺杂使处于BR位置的Eu²⁺的数量上升,而处于mO位置的Eu²⁺的数量下降,抵消了SiN掺杂降低Eu的态密度对光谱的影响．所以适量掺杂的SiN提高了BAM:Eu²⁺荧光粉的吸收发射光谱强度．Si-N键和Eu-N键的Mulliken布居数分别高于Al-O键和Eu-O键, 说明Si-N键和Eu-N键的共价性分别强于Al-O键和Eu-O键．发光中心Eu²⁺局域结构共价性的增强降低了BAM:Eu²⁺镜面层的活性,这是SiN掺杂提高BAM:Eu²⁺+荧光粉光学稳定性的主要原因．     

ELECTRONIC STRUCTURE AND CRYSTALLINE ELECTRIC FIELD IN Rco5(R= Y, La, Ce, Pr, Nd, Sm, Gd, and Tb)

Self consistent charge and spin polarized local spin-density approximation functional theory calculations based on the discrete variational method have been performed for RCo₅(R=Y, La, Ce, Pr, Nd, Sm, Gd, and Tb) compounds. The partial density of states of the Pr atom in the PrCo₆Co₁₂ cluster is established to be strikingly similar to that of the Ce atom in the CeCo₆Co₁₂ cluster, supporting the suggestion that the Pr atom is valence fluctuating. The radii ＜r_4f＞ and ＜r₄f²＞ of the 4f electrons of the R atom from La to Tb, except Ce, show the lanthanide contraction. The crystalline electric field (CEF) parameter A⁰₂ at the R site is calculated using a real charge distribution ρ(R) in the cluster, except for Pr and Nd, and is in agreement with that evalu ated based on the single-ion model. This result shows that the CEF parameter A⁰₂ is mainly determined by the near electronic structure. There exists a hybridization in a certain degree between the light rare-earth R-4f and Co-3d orbitals in some single-electron-molecular-orbitals, which are n ear the Fermi energy level and occupied by electrons. For light rare-earths the R-4f electrons in R Co₆Co₁₂(R=Y, La, Ce, Pr, Nd, and Sm) clu sters are not localized entirely and a small amount of the R-4f electrons have itinerant properties.     

Structural and Electronic Properties of Li2Mg(NH)2 for Hydrogen Storage: First-principles Study

应用第一原理方法研究了储氢材料α-Li₂Mg(NH)₂和β-Li₂Mg(NH)₂两种构型的结构性质和电子性质．计算优化得到的晶胞参数和N-H键长符合实验得到的数据．通过Murnaghan状态方程得到了体积模量和零压力下的能量,计算结果表明α-Li₂Mg(NH)₂为基态构型．通过Mulliken布居分析说明α构型的N-Li/Mg的离子特性和N-H间的交互作用都弱于β构型．态密度分析结果表明,价带轨道主要由N原子的s轨道和p轨道占据,并与H原子的s轨道杂化．     

核裂变中的Overshooting现象与中子多重性

本文采用扩散模型来讨论核裂变中的瞬态过程.研究结果表明在Kramers区域(T/E_f<1)和高温区域((T/E_f>1)瞬态过程的行为差别很大.高温区域瞬态过程中的Overshooting现象会使裂变几率增大,从而使通常认为的裂变速率的瞬态行为引起中子多重性增强效应在这一区域减弱甚至消失.     

Pb-Mg-Al合金腐蚀机理的电子理论研究

为了了解Pb-Mg-Al合金腐蚀的物理本质, 本文采用基于第一性原理的赝势平面波方法系统地计算了Pb-Mg-Al合金中各物相的结合能、费米能级和局域态密度等电子结构参数, 分析了合金的电化学腐蚀机理. 计算结果表明：Pb-Mg-Al合金中各主要组成物相稳定性大小关系为 Mg₁₇Al₁₂>Mg₂Pb>Mg;Mg,Mg₂Pb和Mg₁₇Al₁₂的费米能级存在E_f(Mg)>E_f(Mg₂Pb)>E_f(Mg₁₇Al₁₂)的关系, 说明Mg最容易失去电子, Mg₂Pb次之, Mg₁₇Al₁₂最难;局域态密度表明, 在同样的外界条件下, 体系中Mg相和Mg₂Pb相对于Mg₁₇Al₁₂均处于不稳定的状态, 容易失去电子, 即容易发生腐蚀. Pb-Mg-Al合金体系中不同物相的费米能级差构成了电化学腐蚀的电动势, 导致电子从费米能级高的Mg相和Mg₂Pb相流向费米能级低的Mg₁₇Al₁₂相, 使Pb-Mg-Al合金发生腐蚀.     

Li掺杂8-羟基喹啉铝的密度泛函理论研究

采用密度泛函理论研究了Li原子掺杂8-羟基喹啉铝(Alq₃)分子的几何构型、 前线分子轨道及电子转移特性. 研究结果表明, Li原子掺杂Alq₃后, Li原子与Alq₃的O, N原子键合, 形成电子转移复合物. Li原子将部分电子转移到Alq₃的吡啶环上, 在Alq₃的带隙内形成施主能级, 这种n型掺杂结构有效地提高了电子的传输效率; 但过多的Li原子的掺杂会使Alq₃分解, 从而减弱其电子传输能力. 为使Alq₃的电子传输能力达到最高, Li原子的掺杂应保持在2:1左右的比例.     

掺杂元素对Mg2NiH4稳定性影响的第一性原理研究

本文采用基于密度泛函理论(DFT)的第一原理赝势平面波(PW-PP)方法,计算了低温相Mg2NiH4和(Mg2Ni,X)H4(X=Ag, Al, Ti或Zr)的生成热及电子结构,分析了掺杂元素对Mg2Ni氢化物稳定性的影响. 结果表明,掺杂导致了合金氢化物生成热的绝对值降低,合金氢化物的稳定性下降,且发现掺杂元素电负性越大,氢化物越不稳定. 从电子态密度图和Mulliken布居数分析知道,掺杂后合金氢化物释氢能力增强的主要原因在于Ni-H之间的成键减弱,以及掺杂元素诱导费米能级EF处电子数浓度N(EF)的增加.     

掺杂元素对Mg2NiH4稳定性影响的第一性原理研究

本文采用基于密度泛函理论(DFT)的第一原理赝势平面波(PW-PP)方法,计算了低温相Mg2NiH4和(Mg2Ni,X)H4(X=Ag, Al, Ti或Zr)的生成热及电子结构,分析了掺杂元素对Mg2Ni氢化物稳定性的影响. 结果表明,掺杂导致了合金氢化物生成热的绝对值降低,合金氢化物的稳定性下降,且发现掺杂元素电负性越大,氢化物越不稳定. 从电子态密度图和Mulliken布居数分析知道,掺杂后合金氢化物释氢能力增强的主要原因在于Ni-H之间的成键减弱,以及掺杂元素诱导费米能级EF处电子数浓度N(EF)的增加.     

丰中子奇A核145,147Ce的集体带结构

通过对²⁵²Cf自发裂变产生的瞬发γ谱的测量,对丰中子奇A核^145,147Ce的高自旋态进行了研究,首次识别了¹⁴⁵Ce的集体带结构,扩展了¹⁴⁷Ce的集体带结构,扩展了¹⁴⁷Ce的能级,并新识别了3个边带,粒子–转子模型的计算指出,^145,147Ce的晕带可能来自于νi_13/2轨道的耦合,¹⁴⁵Ce基态起源于(νh_9/2νf_7/2)组态混合,而¹⁴⁷Ce基态则起源于νh_9/2轨道.在这两个核中未观测到明显的八极形变带,然而,在¹⁴⁷Ce中观测到的一个边带,可能显露出八极关联的迹象.     

金属元素替代对Li4BN3H10储氢材料释氢影响机理的第一性原理研究

应用基于密度泛函理论的赝势平面波第一性原理方法研究了金属元素替代对Li₄BN₃H₁₀ 释氢的影响机理.计算给出了结合能、电子态密度、密集数, 分析了结构的稳定性和原子间的成键情况.结果表明: 晶体的结合能与(LiM)₄BN₃H₁₀(M=Ni,Ti,Al,Mg)释氢性能没有直接的关联.带隙的宽窄和带隙中是否存在杂质能级是决定(LiM)< 关键词： LiBNH系储氢材料 第一性原理 元素替代 释氢机理     

Analysis of nuclear spin-lattice relaxation rates in transition metal dihydrides,TMH2 (TM = Sc,Ti, V and Nb) based on LAPW electronic band calculations

The spin-lattice relaxation rates (T _1e T)^?1 of transition metal nuclei ⁴⁵Sc, ⁴⁹Ti, ⁵¹V and ⁹³Nb in cubic dihydrides ScH₂, TiH₂, VH₂ and NbH₂ are calculated on the basis of scalar-relativistic self-consistent LAPW band structure calculations. It is found that the s and p electron contributions to the relaxation rates are negligibly small for all the hydrides studied here due to their very low partial densities of electron states at the Fermi level. The d- orbital contributions are dominant and the core polarization and d-dipolar contributions play a minor role. The theoretical relaxation rates reproduce the experiments very well for ScH₂ and TiH₂ but less satisfactory for VH₂ and NbH₂. The experimental data were taken from our earlier studies and the results of additional measurements on ⁹³Nb in NbH₂ are reported. These have been made in the 30–292K temperature range and at a magnetic field of 7 T.     

Catalytic reduction of NO in the presence of benzene on a Pt(3 3 2) surface

The catalytic reduction of NO in the presence of benzene on the surface of Pt(3 3 2) has been studied using Fourier transform infra red reflection-absorption spectroscopy (FTIR-RAS) and thermal desorption spectroscopy (TDS). IR spectra show that while the presence of benzene molecules at low coverage (e.g., following an exposure of just 0.25 L) promotes NO-Pt interaction, the adsorption of NO on Pt(3 3 2) at higher benzene coverages is suppressed. It is also shown that there are no strong interactions between the adsorbed NO molecules and the benzene itself or benzene-derived hydrocarbons, which can lead to the formation of intermediate species that are essential for N₂ production.TDS results show that the adsorbed benzene molecules undergo dehydrogenation accompanied by hydrogen desorption starting at 300 K and achieving a maximum at 394 K. Subsequent dehydrogenation of the benzene-derived hydrocarbons then begins with hydrogen desorption starting at 500 K. N₂ desorption from NO adlayers on clean Pt(3 3 2) surface becomes significant at temperatures higher than 400 K, giving rise to a peak at 465 K. This peak corresponds to N₂ desorption from NO dissociation on step sites. The presence of benzene promotes N₂ desorption, depending on the benzene coverage. When the benzene exposure is 0.25 L, the N₂ desorption peak at 459 K is dramatically increased. Increasing benzene coverage also results in the intensification of N₂ desorption at ∼410 K. At benzene exposures of 2.4 L, N₂ desorption develops as a broad peak with a maximum at ∼439 K.It is concluded that the catalytic reduction of NO by platinum in the presence of benzene proceeds by NO decomposition and subsequent oxygen removal at temperatures lower than 500 K, and NO dissociation is a rate-limiting step. The contribution of benzene to N₂ desorption is mainly attributed to providing a source of H, which quickly reacts with NO-derived atomic O, leaving the surface with more vacant sites for further NO dissociation.     

MgH2(110)表面Pd单原子催化氢脱附反应的第一性原理研究

本文采用第一性原理密度泛函理论计算研究了MgH₂(110)表面吸附单原子Pd后的氢脱附反应. 计算发现,在吸附一个Pd单原子后,MgH₂(110)表面氢脱附反应的能垒可以从1.802 eV显著地降低到1.154 eV,表明Pd单原子对于氢脱附具有很强的催化效应. 并且,Pd单原子催化还可以将氢脱附的温度从573 K显著地降低到了367 K,从而使MgH₂(110)表面的氢脱附反应更加容易和快速地发生. 此外,通过MgH₂(110)表面氢溢出机制的反向过程来讨论了氢脱附反应的微观过程. 该研究表明Pd/MgH₂薄膜在未来的实验中可作为良好的储氢材料.     

Effect of hydrogen-doping on bonding properties of Ti3SiC2

Using the first principles method based on the density functional theory, we investigated the effect of hydrogen-doping on bonding properties of Ti₃SiC₂. The formation energies of hydrogen interstitials in three possible positions were calculated. The results show that hydrogen favors residing near the (0 0 1) Si plane. In these positions, hydrogen is hybridized most with 1s states of lattice atoms (Si and C), instead of Ti. The presence of hydrogen does not substantially influence the bonding nature of Ti₃SiC₂; chemical bonding is characterized by the hybridizations of Ti d-Si p and Ti d-C p states, and yields high strength. This is contrary to hydrogen-doping in transition metals, where the electron of hydrogen fills in the d bands of the metals and, as a consequence, decreases the cohesive strength of the lattice.     

氧化钒晶体的半导体至金属相变的理论研究

本文利用第一性原理方法研究了金红石相和单斜相VO₂晶体的电子结构和热力学性质.在计算中采用局域密度近似结合Hubbard U模型(LDA+U)描述电子的局域强关联效应,同时也利用微扰密度泛函方法计算了两种相结构的声子谱.计算结果表明V原子3d电子轨道中x²-y²轨道能级分裂决定了VO₂晶体在不同相结构下的金属和绝缘体特性.零温状态方程计算揭示了在68 GPa时可以发生从单斜结构 关键词： 2')" href="#">VO₂ 相变 第一性原理     

Ab initio prediction of half-metallic ferromagnetism in Zn(TM)O2 (TM=Cr,Mn, Fe,Co, Ni) compounds

From the results of first principles tight-binding linear muffin-tin orbital (TB-LMTO) calculations, half-metallic ferromagnetism is proposed in Zn(TM)O₂ with a chalcopyrite structure. The calculated electronic and magnetic property shows that consistent with the integer value for the total magnetic moment, half metallicity is obtained for ZnCrO₂, ZnMnO₂, ZnFeO₂, ZnCoO₂ and ZnNiO₂. A careful analysis of the spin density reveals the ferromagnetic coupling between the p–d states and the cation dangling-bond p states, which is believed to be responsible for the stabilization of the ferromagnetic phase. The calculated heat of formation, bulk modulus and cohesive energy are reported.     

Systematic theoretical investigation of structure and electronic properties of pure copper and lithium doped copper clusters

The pure copper and lithium-doped copper clusters are studied using the unbiased CALYPSO structure searching method and density function theory to understand the evolution of various structure and electronic properties. Theoretical results show the growth behaviours of doped clusters are organised as follows: Li capped Cu_n clusters or Li substituted Cu_n+1 clusters as well as Cu capped Cu_n-1Li clusters. Moreover, the lowest energy structures of Cu_nLi favour planar structures for n ≤ 3 and three-dimensional structures for n = 4–12. In addition, the calculated averaged binding energies, fragmentation energies and second-order difference of energies exhibit obvious odd–even alternations as cluster size increasing. At last, the highest occupied-lowest unoccupied molecular orbital gaps, molecular orbital energy, magnetic property, natural population analysis, natural electron configurations, electrostatic potential, electron density difference, Infrared and Raman spectra and density of states are also, respectively, operative for characterising and rationalising the electronic properties of doped clusters.