YFe2B2电子结构的第一性原理计算

基于密度泛函理论,从头计算了具有ThCr₂Si₂型四方晶系的稀土金属化合物Yfe₂B₂体相的物理特性.能量计算结果表明Yfe₂B₂体相处于顺磁金属态;而能带结构、态密度、布居数以及差分电荷　分布的计算结果表明Y原子的5s,5p电子具有很强的局域性;Fe原子的3d电子和B的1s,2s和2p电子强烈耦合,使得最近邻Fe原子与B原子形成了Fe—B共价键;最近邻的两个Fe原子之间由于 关键词： 稀土金属化合物 第一性原理计算 能带结构 态密度     

内掺过渡金属富勒烯衍生物Ni@C20H20几何结构、成键和电磁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Ni@C₂₀H₂₀的几何结构、成键和电磁性质进行密度泛函计算研究.结构优化发现位于偏离笼子中心三种位置处的Ni原子优化之后均回到笼子中心.结合能和能隙分析表明C₂₀H₂₀的中心位置是Ni原子热力学和动力学最稳定的位置.成键分析表明：Ni原子位于C₂₀H₂₀中心时,和C原子之间几乎没有相互作用,保持自己的孤立状态.电磁分析表明：原子磁矩为2关键词： 20H₂₀')" href="#">C₂₀H₂₀ 20H₂₀')" href="#">Ni@C₂₀H₂₀ 几何结构 成键 电磁性质 密度泛函理论     

锐钛矿相TiO2(101)表面对有机分子不同官能团微观吸附的机制

挥发性有机化合物(VOCs)严重危害了生态环境和人体健康,因此对具有典型官能团的VOCs气体进行灵敏检测具有重要意义.文章研究了具有典型官能团的VOCs气体C₂H₂、C₂H₄、HCOOH、CH₃OH、HCHO和CH₃COCH₃分子在锐钛矿相TiO₂(101)表面吸附的传感特性.结果表明：具有氧空位缺陷的表面对极性分子吸附时,偶极矩越大,吸附体系越稳定;对非极性分子吸附时,C原子成键饱和程度越低,吸附体系越稳定.分析发现,差分电荷密度和电荷布局体现出偶极矩大小和C原子成键饱和程度对气体分子得失电子能力的影响.对于极性分子,气体分子官能团中O原子得到电子的能力为OCH₃COCH₃>OHCHO>OCH₃OH>OHCOOH;对于非极性分子,官能团中C原子得到电子的能力为CC₂H₂>CC     

Ni与钇稳定的氧化锆(111)表面相互作用以及界面活性的第一性原理研究

采用基于密度泛函理论的第一性原理方法, 系统研究了Ni原子在钇稳定的氧化锆(YSZ)(111)和富氧的YSZ(YSZ+O)(111)表面不同位置的吸附, 以及CO和O₂分子在Ni₁(单个镍原子)/YSZ和Ni₁/YSZ+O表面吸附的几何与电子结构特征. 结果表明: 1) 单个Ni原子倾向于吸附在O原子周围, 几乎不吸附在Y原子周围, 且Ni原子在氧空位上吸附最稳定; 2)和YSZ相比, 单个Ni原子在YSZ+O表面易发生氧化现象, Ni原子失去1.06 e电子, 被氧化成了Ni⁺, 吸附能力更强; 3)被氧化的Ni催化活性大幅下降, 大大减弱了表面对O₂和CO等燃料气体的吸附作用.     

C2H2在金刚石（001）-（2×1）重构面上吸附的分子动力学模拟

利用Brenner半经验多体相互作用势和分子动力学模拟方法，研究了乙块（C₂H₂）分子在金刚石（001）-（2×1）重构表面上的碰撞动力学过程与化学吸附构型的关系.观察到C₂H₂在金刚石表面的6种吸附结构.约95％的吸附呈C₂H₂与表面形成两个σ单键的形式.讨论了轰击能量、入射位置及金刚石表面原子的空间位形对各种吸附构型形成的影响.还给出了化学吸附过程的分子快照，并讨论了C₂H₂分子与表面的能量交换关系. 关键词：     

Li修饰的C24团簇的储氢性能

利用密度泛函理论研究了Li原子修饰的C₂₄团簇的储氢性能. Li原子在C₂₄团簇表面的最佳结合位是五元环. Li原子与C₂₄团簇之间的作用强于Li原子之间的相互作用, 能阻止它们在团簇表面发生聚集. 当Li原子结合到C₂₄表面时, 它们向C原子转移电子后带正电荷. 当氢分子接近这些Li原子时, 在电场作用下发生极化, 通过静电相互作用吸附在Li原子周围. 在Li修饰的C₂₄复合物中, 每个Li原子能吸附两到三个氢分子, 平均吸附能处于0.08到0.13 eV/H₂范围内. C₂₄Li₆能吸附12个氢分子, 储氢密度达到6.8 wt%.     

Mg原子修饰的封闭型六硼烷B6H62-储氢性质的研究

利用密度泛函理论的方法研究了Mg原子修饰的封闭型六 硼烷B₆H₆^2-吸附氢的性能. Mg可以稳定地结合在B₆H₆^2-上, 它可以吸附六个氢分子. 电荷转移所导致的Mg周围电场的增强和体系更大的偶极矩使 得MgB₆H₆^2-比MgB₆H₆具有更好的储氢性能, 储氢密度达到11.1 wt%, 氢分子的平均结合能在0.23 eV/H₂至0.34 eV/H₂之间. 结果表明可以通过控制金属-有机物体系的电荷态来增强电场, 进而改善其储氢性能. 关键词： 6H₆^2-团簇')" href="#">MgB₆H₆^2-团簇 密度泛函理论(DFT) 储氢性能 电荷态     

B2H6分子的几何构型

采用Gaussian 98程序中B3P86，BP86，B3LYP，BLYP，UHF，HF及LSDA等方法，对B_{2Ｈ6分子可能的D3d，D3h，D2d和D2h平面型状态及立体型状态 的几何构型五种情况的1重态及3重态进行了优化，得到该分子基态为1重态，它的电子状态 是^lＡg,B2H6的几何构型仍然是传统的对 称性为乙烯式的D2h结构 ，其构型如图9所示，其能量最低，是－53．5865H.a.u..两个硼原子与四个H原子所在平面 垂直于两个硼原子及另外二个H原子所在平面，二个硼原子之间的距离是R12=0 ．17542nm，B原子及H原子之间的距离是R17=0．13149nm，R13=0． 1188 4nm,它们之间的夹角分别是，∠314=∠526=121．93°，∠817=∠827=96．3°，B2Ｈ6中硼原子采用不等性的sp³轨道和另一硼原子的不等性的sp< sup>3轨道 及氢原子的1s轨道 交互重叠生成桥式三中心双电子键.三中心双电子键比双中心双电子键更为稳定，计算结果 也证实了这一点. 关键词： 2H6')" href="#">B2H6 密度泛函 几何构型 优化}     

NH3分子在LiH（100）表面吸附的第一性原理研究

采用第一性原理方法研究了NH₃分子在LiH（100）晶面的表面吸附情况.通过研究LiH（100）/NH₃体系的吸附位置、吸附能和电子结构,发现NH₃分子在LiH（100）晶面主要是化学吸附,初始位置为NH₃分子中N-H键在Li顶住时失去一个H原子,并在LiH（100）面形成NH₂基,其吸附能为0.511 eV,属于强化学吸附,吸附作用最强.此时NH₂基与附近H原子和Li原子之间为离子键作用,NH₂基中N—H键为共价键;NH₃分子中另一个H原子与LiH表面的一个H原子形成一个H₂分子逸出表面.H₂分子中H-H键为明显的共价键.     

CO2在金属有机骨架材料有机链上的吸附机理研究

金属有机骨架是一种新型的温室气体CO₂吸附材料。本文采用密度泛函理论（DFT）方法研究CO₂在MOF-5有机链上的6种不同吸附位置及其3种不同构型下的吸附行为。考虑GGA水平下三种不同泛函对计算结果的影响,对比发现GGA/PW91泛函能够较好地计算CO₂分子与有机链原子之间的弱范德华力;发现CO₂分子与苯环边相交以及与苯环上的碳原子平行是两种吸附能最大的构型;利用Br原子替代苯环上的H原子可以显著增强对CO₂分子的吸附能力,为设计具有较高CO₂吸附能力的MOFs材料提供理论依据。     

High-resolution electron microscopy study of Ni81Fe19 film with Co33Cr67 buffer layer

The anisotropic magnetoresistance (AMR) in permalloy Ni₈₁Fe₁₉ film deposited on a 1.2 nm Co₃₃Cr₆₇ buffer layer was significantly enhanced. The high-resolution electron microscopy was used to study the microstructure of Ni₈₁Fe₁₉ film with and without Co₃₃Cr₆₇ buffer layer. It was found that Co₃₃Cr₆₇ buffer layer can induce good (1 1 1) texture, while without Co₃₃Cr₆₇ buffer layer, Ni₈₁Fe₁₉ film show randomly oriented grain structure. The Δρ/ρ enhancement is attributed to the decrease in the resistivity ρ of the Ni₈₁Fe₁₉ film due to the formation of the large (1 1 1) textured grains in Ni₈₁Fe₁₉ film with Co₃₃Cr₆₇ buffer layer. However, the surface roughness of substrate may limit the (1 1 1) textured grain size and induce additional grain boundaries in Ni₈₁Fe₁₉ film with Co₃₃Cr₆₇ buffer layer, limit the enhancement of the AMR effect.     

Theoretical study of interaction between atoms of Au, Ag, Cu and clean Si(1 1 1) surface

To evaluate the interactions between the atoms of Au, Ag and Cu and clean Si(1 1 1) surface, two types of silicon clusters Si₄H₇ and Si₁₆H₂₀ together with their metal complexes were studied by using hybrid (U)B3LYP density functional theory method. Optimized geometries and energies on different adsorption sites indicate that: (1) the binding energies at different adsorption sites are large (ranging from 1.2 to 2.6 eV depend on the metal atoms and adsorption sites), suggesting a strong interaction between metal atom and silicon surface; (2) the most favorable adsorption site is the on top (T) site. Mulliken population analysis indicated that in the system of on top (T) site, a covalent bond is formed between metal atom and dangling bond of surface Si atom.     

石墨烯在Al_2O_3(0001)表面生长的模拟研究

基于密度泛函理论的广义梯度近似法,对用化学气相沉积法在蓝宝石(α-Al_2O_3)(0001)表面上生长石墨烯进行理论研究.研究结果表明:CH_4在α-Al_2O_3(0001)表面上的分解是吸热过程,由CH_4完全分解出C需要较高能量及反应能垒,这些因素不利于C在衬底表面的存在.在α-Al_2O_3(0001)表面,石墨烯形核的活跃因子并不是通常认为的C原子,而是CH基团.通过CH基团在α-Al_2O_3(0001)表面上的迁移聚集首先形成能量较低的(CH)_x结构.模拟研究(CH)_x对揭示后续石墨烯的形核生长机理具有重要意义.     

Adsorption of N2 and N2O on Ni(7 5 5) surface: ab initio periodic density functional study

Adsorption of N₂ and N₂O at various sites on Ni(7 5 5) has been investigated by density functional theory (DFT) method (periodic DMol³). Several possible adsorption structures (attaching the nitrogen atom to the surface, or lying parallel) are found for both molecules. There is a clear binding energy preference of N₂ and N₂O for step sites in contrast to the case of CO. It is revealed that the decomposition of N₂O occurs exclusively near the step, but not on the terrace. Two decomposition channels can be considered; dissociative adsorption and spontaneous decomposition during TPD ramp. Three possible candidates for the precursor of the spontaneous decomposition of N₂O during TPD ramp are discussed.     

C2H4/Ni(100)近边X射线吸收谱的多重散射理论研究

本文用多重散射原子集团方法计算并分析了C₂H₄/Ni(100)系统的碳K边近边X射线吸收精细结构(NEXAFS)谱,确定了乙烯吸附在Ni(100)表面上的几何结构。结果表明,乙烯是吸附在垂直桥位上的,其中碳原子与表面最近的镍原子距离是1.70?,而乙烯分子平面倾斜于表面50°,同时发现,氢和镍之间的相互作用对结构的形成有很大的作用,这些结果得到了不同途径的验证。 关键词：     

Kinetic interface roughening and magneto resistance of sputter-deposited Fe/Ni75B25 multilayers

The roughening of interfaces as a function of layer thickness and magneto transport properties have been investigated on sputter-deposited Fe/Ni₇₅B₂₅ multilayer films. X-ray reflectivity data were recorded for Ni₇₅B₂₅(72 nm) film and for [Fe(2 nm)/Ni₇₅B₂₅(2 nm)]₁₆ and [Fe(4 nm)/Ni₇₅B₂₅(4 nm)]₈ multilayer films. A power law dependence of the interfacial width of growing Fe/Ni₇₅B₂₅ interfaces was observed. The resulting growth exponents β were found to be in the range of 0.55–0.58 in the initial growth stage of the multilayer with lower Fe/Ni₇₅B₂₅ repetition thickness and at approximately 0.34 for multilayer with higher repetition thickness. The growth exponents were compared with theoretical calculations. High resolution electron microscopy revealed the columnar growth of the Fe/Ni₇₅B₂₅ multilayer. Additionally, an increase of magnetoresistance was observed by the multilayering of Ni₇₅B₂₅ films with Fe interlayers.     

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.     

Investigation of the role of oxygen in NO reduction by C2H4 on the surface of stepped Pt(3 3 2)

The influence of pre-dosed oxygen on NO–C₂H₄ interactions on the surface of stepped Pt(3 3 2) has been investigated using Fourier transform infrared reflection–absorption spectroscopy (FTIR-RAS) and thermal desorption spectroscopy (TDS). The presence of oxygen significantly suppresses the adsorption of NO on the steps of Pt(3 3 2), leading to a very specific adsorption state for NO molecules when oxygen–NO co-adlayers are annealed to 350 K (assigned as atop NO on step edges). An oxygen-exchange reaction also takes place between these two kinds of adsorbed molecules, but there appears to be no other chemical reaction, which can result in the formation of higher-valence NOx.

C₂H₄ molecules which are post-dosed at 250 K to adlayers consisting of ¹⁸O and NO do not have strong interactions with either the NO or the ¹⁸O atoms. In particular, interactions which may result in the formation of new surface species that are intermediates for N₂ production appear to be absent. However, C₂H₄ is oxidized to C¹⁸O₂ by ¹⁸O atoms at higher annealing temperature. This reaction scavenges surface ¹⁸O atoms quickly, and the adsorption of NO molecules on step sites is therefore quickly restored. As a consequence, NO dissociation on steps proceeds very effectively, giving rise to N₂ desorption which closely resembles that following only NO exposure on a clean Pt(3 3 2), both in peak intensity and desorption temperature. It is concluded that the presence of ¹⁸O₂ in the selective catalytic reduction (SCR) of NO with C₂H₄ on the surface of Pt(3 3 2) does not play a role of activating reactants.