硼原子掺杂对碳纳米管吸附Ne原子影响的第一性原理计算

采用基于第一性原理的密度泛函理论(DFT)和局域密度近似(LDA)方法,优化计算得到碳纳米管(CNT),硼原子取代碳原子及其吸附氖原子前后系统的几何结构,能量,电子能带和态密度.结果显示,碳纳米管的能带结构与石墨的层状几何结构相似,能量的变化只在kz=0和kz=0.5平面之间沿着c轴方向出现.B原子取代C原子使价带和导带分别分裂为两个和三个能带.对Ne原子的吸附使价带能量沿着c轴方向升高并导致Fermi面附近的态密度下降.Ne原子的吸附在谷位H最稳定,顶位A其次.C-C间σ键的弯曲使Ne原子吸附在桥位b1比桥位b2处更为稳定.Ne原子在管外的吸附均为放热过程,而管内则为吸热过程.结构分析表明Ne原子对C原子有排斥作用,对B原子却具有吸引作用.B原子取代C原子的位置略凸出于CNT的管壁之外,使Ne原子的吸附能增加.     

H在Al(111)面上吸附的多重散射X_α自洽计算

利用多重散射X_α自洽场方法研究了H在Al(111)表面吸附的桥位和顶位模型。结果表明顶位吸附的结合能优于桥位。顶位吸附中H的1s电子与Al相互作用形成不同形式的σ键,本文分析了这些成键细节,并给出了顶位吸附的态密度。     

硼原子掺杂对碳纳米管吸附Ne原子影响的第一性原理计算

采用基于第一性原理的密度泛函理论（DFT）和局域密度近似（LDA）方法,优化计算得到碳纳米管（CNT）,硼原子取代碳原子及其吸附氖原子前后系统的几何结构,能量,电子能带和态密度。结果显示,碳纳米管的能带结构与石墨的层状几何结构相似,能量的变化只在kz=0和kz=0.5平面之间沿着c轴方向出现。B原子取代C原子使价带和导带分别分裂为两个和三个能带。对Ne原子的吸附使价带能量沿着c轴方向升高并导致Fermi面附近的态密度下降。Ne原子的吸附在谷位H最稳定,顶位A其次。C-C间σ键的弯曲使Ne原子吸附在桥位b1比桥位b2处更为稳定。Ne原子在管外的吸附均为放热过程,而管内则为吸热过程。结构分析表明Ne原子对C原子有排斥作用,对B原子却具有吸引作用。B原子取代C原子的位置略凸出于CNT的管壁之外,使Ne原子的吸附能增加。     

硼原子掺杂对碳纳米管吸附Ne原子影响的第一性原理计算

采用基于第一性原理的密度泛函理论（DFT）和局域密度近似（LDA）方法，优化计算得到碳纳米管（CNT），硼原子取代碳原子及其吸附氖原子前后系统的几何结构，能量，电子能带和态密度。结果显示，碳纳米管的能带结构与石墨的层状几何结构相似，能量的变化只在kz=0和kz=0.5平面之间沿着c轴方向出现。B原子取代C原子使价带和导带分别分裂为两个和三个能带。对Ne原子的吸附使价带能量沿着c轴方向升高并导致Fermi面附近的态密度下降。Ne原子的吸附在谷位H最稳定，顶位A其次。C-C间σ键的弯曲使Ne原子吸附在桥位b1比桥位b2处更为稳定。Ne原子在管外的吸附均为放热过程，而管内则为吸热过程。结构分析表明Ne原子对C原子有排斥作用，对B原子却具有吸引作用。B原子取代C原子的位置略凸出于CNT的管壁之外，使Ne原子的吸附能增加。     

H在Al(111)面上吸附的多重散射Xα自洽计算

利用多重散射X_α自洽场方法研究了H在Al(111)表面吸附的桥位和顶位模型。结果表明顶位吸附的结合能优于桥位。顶位吸附中H的1s电子与Al相互作用形成不同形式的σ键,本文分析了这些成键细节,并给出了顶位吸附的态密度。 关键词：     

N掺杂碳纳米管环吸附Fe原子的第一性原理研究

采用基于密度泛函理论的CASTEP程序研究N掺杂碳纳米管环结构在变形作用下,外壁对Fe原子的吸附能力.结果表明,构造出的新型纳米结构的结合能为负值,具有稳定存在的可能性;N掺杂碳纳米管环显著提高外壁对Fe原子的吸附能力,这是因为掺杂体系的活度增大,易与Fe原子间形成Fe-N共价结合键.线性增加拉伸和压缩变形幅度,结构外壁对Fe原子的吸附能呈抛物线式快速下降.相比之下,吸附能对拉伸变形更加敏感.     

缺陷碳纳米管限域金属Ti原子的理论研究

基于密度泛函第一性原理研究了金属原子Ti在原始、单空位缺陷(SV)、Stone-Wales(SW)缺陷碳纳米管内外的吸附情况.我们的计算结果表明金属Ti原子在缺陷碳纳米管内外结合能的排列顺序为:SVSW-zSW-xpristine(外吸附),SVSW-xSW-zpristine(内吸附).同时,我们通过吸附结构、电子密度和态密度等分析了Ti原子与碳纳米管的作用机制.其中,SV缺陷碳纳米管由于失去一个碳原子而形成了的三个悬键具有很强的结合能力,金属原子Ti在SV缺陷碳纳米管内外的吸附能力都是最强的.对于SW缺陷的碳纳米管,由于缺陷的位置不同,对于金属原子Ti内外吸附的能力也是不同的.因此,缺陷的存在能调节碳纳米管载体对Ti原子的吸附性能.     

P掺杂单壁硅纳米管Mg原子吸附性能的第一性原理研究

采用密度泛函理论的广义梯度近似和平面波赝势方法,研究P掺杂单壁硅纳米管对Mg原子的吸附性能.计算本征、掺杂P、施加形变作用（压缩和拉伸）的（6,6）硅纳米管外壁对Mg原子的吸附能,分析掺杂P前后的成键情况及电荷布局数.结果表明,掺杂P使体系形成Mg-P和Si-P间的离子性键,增强了Si-Si间的离子性键,P掺杂硅纳米管超晶格中离子键与共价键共存;掺杂P后显著提高了硅纳米管外壁对Mg原子的吸附能力;硅纳米管外壁对Mg原子的吸附能在0.25%,0.50%,1.00%,1.25%的压缩量和1.00%,1.25%的拉伸量时增大,可显著增强硅纳米管材料作为增强相时与基体界面间结合的粘附性.     

外加电场作用下碳纳米管结构稳定性及结构修饰研究

利用外加电场的方法，对多壁碳纳米管的结构稳定性进行了研究.结果表明当场强达到30 V/nm时，碳纳米管端部的结构失稳，端部碳原子间的π键被打开，外部原子开始进入到碳纳米管的结构中.利用电子显微镜作为纳米加工仪器，通过外加电场的方法在多壁碳纳米管的端部制备了非晶态碳纳米线，形成碳纳米管-纳米线复合结构.碳纳米管和纳米线结合处的σ键作为绝缘界面，形成了电子输运的势垒.     

金原子掺杂的碳纳米管吸附CO气体的密度泛函理论研究

鉴于碳纳米管复合材料具有较强气敏性,该性质对于指导剧毒气体探测器的研发具有重要意义,因此,本文采用密度泛函方法对CO气体在本征、金原子掺杂(8,0)单壁碳纳米管的吸附行为进行研究. 通过对吸附体系的几何、电子结构研究表明,CO分子在金原子掺杂的碳纳米管外壁的金原子位置处的吸附能力远大于CO在本征碳纳米管处的吸附,此外,还计算了两种典型位置的电子密度、态密度,进一步支持了掺金碳纳米管对CO气体具有超强的敏感性,因此,金原子掺杂的碳纳米管有望成为探测CO气体的新一代气敏元件. 关键词： 碳纳米管 CO 金原子 掺杂     

MD investigation of the collective carbon atom behavior of a (17, 0) zigzag single wall carbon nanotube under axial tensile strain

The collective dynamic behavior of carbon atoms of a (17, 0) zigzag single wall carbon nanotube is investigated under tensile strains by molecular dynamics (MD) simulations. The “slip vector” parameter is used to study the collective motion of a group of atoms and the deformation behavior in three different directions (axial, radial, and tangential) of a (17, 0) carbon nanotube. The variations of radial slip vectors indicate almost all carbon atoms of the (17, 0) carbon nanotube will stay on the cylindrical surface before the yielding of the single wall carbon nanotube (SWNT). Furthermore, the tangential vectors show kinking deformation for the (17, 0) zigzag tube only rarely appears when the crack occurs. Non-symmetrical deformation around a carbon atom along the axial direction also can be found. The variations in the slip vector values of each atom display a symmetrical crack along the horizontal direction and normal to the tube axis. Chain-like structures with 3–4 atoms can be observed, with the number of chain-like structures decreasing before the breakage of the SWNT. The mechanical properties and dynamic behavior of a (17, 0) zigzag SWNT under tensile strain are also compared with that of a (10, 10) armchair tube in our previous study (Weng et al. 2009).     

Dependence of in—tube doping on the radius and helicity of single—wall carbon nanotubes

Using the Lennard－Jones interaction potential between the impurity atom and carbon atom, we have studied the dependence of in-tube impurity doping on the radius of a single-wall carbon nanotube (SWNT), as well as its helicity. The obtained results show that the radius of the most stably doped SWNT is different for different kinds of impurity atoms. This is useful for producing the required doped SWNT. In addition, it is found that the helicity of tube has a strong effect on the potential energy of the atoms doped in the SWNT.     

Interaction of hydrogen molecules on Ni-doped single-walled carbon nanotube

Adsorption of hydrogen molecules on an Ni-doped (8,0) single-walled carbon nanotube (SWNT) is investigated by using first-principles density functional calculations. The result shows that a single Ni atom adsorbed on the bridge site of the tube could cannot dissociate the H₂, however it can chemisorb three H₂ at most, with the average binding energy per H₂ suitable for the hydrogen storage at the room temperature. More H₂ would physisorb around an Ni atom weakly. As for the SWNT with an Ni dimer adsorbed, we find that when the H₂ approaches the Ni--Ni bond, it dissociates without overcoming any barrier and makes bonds with Ni atom.     

First-principles study of palladium atom adsorption on the boron- or nitrogen-doped carbon nanotubes

We have performed first-principles calculation to investigate the adsorption of a single palladium atom on the surface of the pristine and boron- or nitrogen-doped carbon nanotubes (CNTs). The results show that for the adsorption of a single palladium atom on the pristine CNT surface, the most stable site is Bridge1 site above the axial carbon–carbon bond. Either boron- or nitrogen-doped CNTs can assist palladium surface adsorption, but the detailed mechanisms are different. The enhanced palladium adsorption on boron-doped CNT is attributed to the palladium d orbital strongly hybridized with both boron p orbital and carbon p orbital. The enhancement in palladium adsorption on nitrogen-doped CNT results from activating the nitrogen-neighboring carbon atoms due to the large electron affinity of nitrogen. Furthermore, the axial bond is preferred over the zigzag bond for a palladium atom adsorbed on the surface of all three types of CNTs. The most energetically favorable site for a palladium atom adsorbed on three types of CNTs is above the axial boron–carbon bond in boron-doped CNT. The enhancement in palladium adsorption is more significant for the boron-doped CNT than it is for nitrogen-doped CNT with a similar configuration. So we conclude that accordingly, the preferred adsorption site is determined by the competition between the electron affinity of doped and adsorbed atoms and preferred degree of the axial bond over the zigzag bond.     

The effect of hydrogen and oxygen atoms on the adsorbed gallium inside defective carbon nanotubes

The adsorption of single gallium atoms on the inner walls of single-walled carbon nanotubes with hydrogen/oxygen-saturated monovacancies are studied by using the density functional theory method. When the monovacancy is saturated by the hydrogen or oxygen atom, the gallium atom prefers to adsorb on the top of the center of a pentagon ring, and the binding energy between the gallium atom and carbon nanotube is significantly lower as compared to the case with a pure monovacancy. In addition, the results of the density of states show that the states originating from the adsorbed gallium atoms shift toward lower energy when the carbon atoms with dangling bonds are saturated by hydrogen or oxygen atoms. Meanwhile, these states have no contribution to the states near the Fermi levels.     

BTA在铜表面吸附的密度泛函理论研究

本文基于密度泛函理论(DFT)的第一性原理研究了苯并三氮唑(BTA)分子吸附于铜表面的反应活性特征及其吸附在三种不同取向晶面时的电荷转移以及成键情况,结果表明：BTA分子的亲电和亲核活性中心为N(1)、N(2)和C(5),在铜表面垂直吸附时为化学吸附,Cu原子的最外层价电子转移到N(2)原子上,两者形成配位键;BTA分子在三种不同取向的铜表面吸附时的吸附能大小为：Cu(110)_x>Cu(100)_x>Cu(111)_x(x=T、B、H),T表示顶位,B表示桥位,H表示空位;BTA吸附在Cu(111)面的转移电荷量：T(顶位)>B(桥位)>H(空位).     

CuPc/ITO结构的表面和界面电子态的XPS研究

覆盖有Indium tin oxide(ITO)膜的透明导电玻璃广泛地用作有机发光器件 (OLEDs)的空穴注入电极 ,但是ITO膜的功函数通常与空穴传输材料的最高被占据分子轨道 (HOMO)不匹配。铜酞菁 (CuPc)作为缓冲层可以提高空穴从ITO向空穴传输材料的注入效率。对CuPc ITO样品的XPS表面分析表明 ,在CuPc分子中 ,铜原子显 2价 ,通过配位键和氮原子相互作用。CuPc分子中有两类碳原子 :8个C原子与 2个N原子成键 ;其余 2 4个C原子具有芳香烃性质。N原子也处在两种化学环境中 :有 4个N原子只与 2个C原子形成CNC键 ;另外 4个N原子不仅与 2个C原子成键 ,还通过配位键与Cu原子成键。用氩离子束对样品表面进行了溅射剥蚀 ,当溅射时间分别为 2 ,5 ,10min时进行XPS采谱分析 ,结果表明 ,随着氩离子束溅射时间增长 ,C 1s,N 1s峰变弱 ,Cu 2p ,O 1s,In 3d,Sn 3d峰增强 ,C 1s,N 1s,O 1s,In 3d和Sn 3d峰都向高束缚能或低束缚能方向移动 ,但它们的情况却不相同。     

热效应对纳米焊接界面结构的影响

采用分子动力学方法深入研究热效应对纳米焊接界面结构的影响。具体分析了碳管直径和时间的变化对界面结构的影响规律,并详细给出了1530 K下的焊接过程。结果表明,除碳管(5,5)外,碳管(6,6),(7,7),(9,9),(11,11)中纳米线形成的时间分别为13.8, 14.6, 17.5, 19.6 ps。纳米线是由单根或多根Ni原子链组成,碳管(6,6),(7,7),(9,9),(11,11)中Ni原子链数分别为1,3,7和16。界面结构包括内部焊接和外部焊接。内部焊接的临界直径由碳管(6,6)决定,其值为0.814 nm。在同一时刻,大直径的碳管可获得更大的外部接触长度。外部接触长度的增长速率随碳管直径的增加而增大,接触长度的最大增长速率可达0.013 nm/ps。最后确定了界面结构形成临界温度,发现对于相同直径碳管,外部焊接的临界温度高于内部焊接的临界温度,临界温度与碳管直径无关。     

Giant thermopower effects from molecular physisorption on carbon nanotubes

Results are presented of in situ studies of the thermoelectric power and four-probe resistance of single-walled carbon nanotube films during the adsorption of cyclic hydrocarbons C(6)H(2n) (n=3-6). The size of the change in these transport parameters is found to be related to the pi electron population of the molecule, suggesting the coupling between these pi electrons and those in the nanotube wall may be responsible for the observed effects. A transport model for the SWNT film behavior is presented, incorporating the effects of a new scattering channel associated with the adsorbed molecules.