Geometric and electronic structures of B12C6N6 fullerene

An electron deficient fullerene B₁₂C₆N₆ is studied by using ab initio calculations. The structure is generated by replacing N with C in the B₁₂N₁₂ cage to ensure only B–C and B–N bonds are formed. All the possible isomers are optimized and the low energy structures are determined. C and N atoms in the low energy isomers are inclined to segregate and form B₂C₂ and B₂N₂ squares. Natural bond analysis shows that the atomic orbitals of B, C and N in this cage hybrid approximately in sp^2.3 and then form B–C and B–N bonds. The 2p orbitals perpendicular to the cage surface are partially occupied and the molecular orbitals formed by these orbitals are highly delocalized. The natural charge on N is about −1.17 in both B₁₂N₁₂ and B₁₂C₆N₆, and the charge on C is −0.72 to −0.60. The molecular orbital compositions show that the B–N bonds are the same in B₁₂N₁₂ and B₁₂C₆N₆, and the B–C bonds possess stronger covalent character. The HOMO of B₁₂C₆N₆ is formed by 2p of B and C, and the LUMO is formed by 2p of C. The energy gap of C₂₄, B₁₂N₁₂ and B₁₂C₆N₆ is 2.52, 6.84 and 3.22 eV, respectively.     

Al12N、Al12B团簇结构和电子性质的密度泛函计算

利用密度泛函理论研究了Al12N和Al12B团簇的原子结构和电子性质,通过各种异构体的比较,发现两种掺杂团簇的最低能量结构都是完好的二十面体(Ih)结构,N(B)原子占据在二十面体的中心.高对称性团簇形成稀疏离散的电子态密度和大的电子能隙.在Al-N之间发生较大的电荷转移.因此我们建议把Al12N团簇看作是碱金属超原子,Al12B团簇看作是卤素超原子,用来构造团簇组装固体.     

A study of the electronic and structural properties of C28 and C16N12

Equilibrium geometry of the heterofullerene C₁₆N₁₂ is calculated at the Density Functional Theory level and further compared with that of fullerene C₂₈. Theoretical vibrational spectra as well as the infrared intensities and Raman activities are reported. In addition, the effect of N substitution on fullerene stability is investigated in comparison to exohedral complexes C₂₈Cl₄ and C₁₆N₁₂Cl₄. The results show that C₁₆N₁₂ is stabilized by strengthening the hexagon belts, while exohedral complexes stabilize the hexagon structure.     

外掺非典型富勒烯C64Si的几何结构和电子性质计算研究

采用密度泛函理论(density functional theory, DFT)中的广义梯度近似(generalized gradient approximation, GGA)对非典型富勒烯C64Si的几何结构和电子性质进行计算研究,发现在C64Si可能稳定存在的四种同分异构体中,Si原子吸附在三个直接相邻五边形的公共原子处形成的外掺杂结构是热力学最稳定的结构,即文中定义的C64Si-1,这和Ge等人对 Si原子在C28笼子外部最稳定位置的预测相一致.通过对C64Si-1的能级图、轨道分布和态密度图的分析可知:Si原子的原子轨道对电子最低未占据轨道的贡献比较大,而对电子最高占据轨道的贡献比较小,但是Si原子的局部态密度对C64Si-1整体态密度的影响非常小.对C64Si-1的亲和能和电离能分析得知:外掺Si原子之后,笼子的得电子能力和失电子能力都有所降低.     

Silver oligomer and single fullerene electronic properties revealed by a scanning tunnelling microscope

Clusters on surfaces have been investigated with low-temperature scanning tunnelling microscopy and spectroscopy. Constant current spectra acquired on Ag oligomers and one-dimensional chains on a Ag(111) reveal a single resonance peak whose energy shifts towards the Fermi level with increasing cluster size. Next, controlled and reproducible contact between a STM tip and a C₆₀ molecule adsorbed on Cu(100) is reported. The transition from tunnelling to contact is discussed in terms of local heating of the tip-molecule junction.     

Orientation effect on the electronic transport properties of C24 fullerene molecule

The transport properties of the cage-like molecule depend on its orientation between the electrodes, but the investigation on the mechanism has not been found. Using first-principle density-functional theory (DFT) and non-equilibrium Green’s function (NEGF) formalism for quantum transport calculation, we study the electronic transport properties of C₂₄ fullerene molecule with different orientations in Au–C₂₄–Au two-probe system. The effects of k-point sampling on the Brillouin zone are explored. Our results show that the negative differential resistance of C₂₄ molecule is found in such a system and can be tuned by the molecule's orientation in the two-probe system. We also proposed a mechanism for it. The I–V characteristic under bias voltage is determined. The present findings could be helpful for the application of the C₂₄ molecule in the field of single molecular devices or nanometer electronics.     

C40富勒烯分子的电子结构与传输特性研究

本文采用密度泛涵理论对富勒烯C₄₀分子进行了结构优化,得到了稳定构型,然后构建了以金原子面为电极的电子输运模型.使用非平衡格林函数方法对构建的电子输运模型进行了电子输运性质的计算,得到了电子透射谱和伏安曲线,并分析了分子器件产生电子输运性质的原因.研究结果发现:C₄₀富勒烯的化学活性明显强于富勒烯C₆₀和C₃₂分子,在一些分子能级处,该分子为一个良导体.     

C50富勒烯分子的电子结构与传输特性研究

本文构建了Au原子面为电极的富勒烯C₅₀分子的电子输运模型,使用非平衡格林函数方对构建的以Au原子面为电极的C₅₀分子的电子输运模型进行了电子传输性质的计算.通过计算得出了电子透射谱、电导曲线和电流电压曲线,分析了此分子器件产生电子输运性质的原因.研究计算结果发现:C₅₀分子具有量子器件的开关特性,并具有明显的半导体特征.     

C40富勒烯分子的电子结构与传输特性研究

本文采用密度泛涵理论对富勒烯C40分子进行了结构优化,得到了稳定构型,然后构建了以金原子面为电极的电子输运模型．使用非平衡格林函数方法对构建的电子输运模型进行了电子输运性质的计算,得到了电子透射谱和伏安曲线,并分析了分子器件产生电子输运性质的原因. 研究结果发现：C40富勒烯的化学活性明显强于富勒烯C60和C32分子,在一些分子能级处,该分子为一个良导体．     

富勒稀C36的电子结构与电子传导

本文采用基于第一性原理的密度泛函理论和非平衡格林函数方法研究了C36分子的电子结构和电子传导特性．本文以Au(1,1,1)为电极分别建立了4个电子输运模型,分别计算了他们的电子传输概率、伏安曲线,同时分析了产生这些分子器件电子输运性质的原因．研究计算结果发现, C36的电子输运主要发生在分子壳上,当左、右电极分别连接在第6号和第35号碳原子两端时,C36的电子输运性能最好,伏安曲线显示该分子具有半导体特性．     

Location of muonium and hydrogen in C60 fullerene and associated electronic structure and hyperfine properties

The unrestricted Hartree-Fock (UHF) procedure is used to investigate the locations, associated electronic structures and hyperfine interactions for muonium and hydrogen in C₆₀ fullerene. Our results indicate that from total energy considerations, in keeping with earlier investigations, the exohedral model has the lowest energy. However, the energies of the endohedral model involving the muonium (hydrogen) inside the fullerene and bonded to one of the carbon atoms, and of the muon at the center are found to be almost equal, contrary to earlier results. The hyperfine interaction constant for the endohedral site is in good agreement with that required to explain the lower observed muon spin-rotation (SR) frequency in the C₆₀-muonium system. The same appears to be the case for the exohedral model. However, there seems to be some uncertainty about the theoretical result in the latter case due to significant admixtures of higher spin states in the UHF wave-function. Additionally, in solid fullerene, the calculated location of the muonium for the exohedral model is such that it could be bonded to two fullerene molecules and therefore a muonium attached to a simple fullerene may not be representative of the exohedral state. This feature as well as the difficulty for the exohedral model of explaining the observed equality of the correlation times for relaxation effects associated with both SR and¹³C relaxation times in nuclear magnetic resonance (NMR) experiments suggests that the endohedral model for muonium cannot at present be ruled out as a viable model in favor of the exohedral model. Possible avenues for future investigations to resolve some of the problems for both exohedral and endohedral models are discussed. Results obtained for muonium at the center of fullerene are presented and compared to the features of the observed high frequency SR signal, and possible improvements in theory are discussed.     

电场作用下S修饰C24N24从CO2/N2混合气体中选择性吸附

在燃烧后气体中选择性捕获CO2,对减缓因CO2浓度过高引发的环境问题具有十分重要的意义。本文采用第一性原理计算的方法,研究了外加电场作用下S修饰C24N24富勒烯对CO2的选择性吸附性能。首先研究了S@C24N24的结构和性质,发现其具有良好的稳定性。其次,研究了无电场时S修饰C24N24富勒烯对CO2的吸附行为,发现其吸附为弱的物理吸附。另外,进一步研究了外加电场作用下S@C24N24对CO2的吸附行为。结果表明,结合距离（CO2与S）和CO2的键角（O=C=O）随电场的增大而减小;当电场增加到0.018 au时,物理吸附转变为化学吸附。关闭电场时,化学吸附又转化为物理吸附。此外,即使在相同的电场条件下,S修饰C24N24富勒烯对N2的吸附也为弱的物理吸附。这表明,通过控制外加电场的开/关,S@C24N24可以从CO2/N2混合气体中选择性捕获/释放CO2,可作为选择性捕获CO2的优良候选材料。     

Time-dependent Hartree-Fock calculation of 12C + 12C with a realistic potential

We have used a realistic single-panicle K-matrix model to compute the head-on scattering of ¹²C + ¹²C at incident projectile lab energies of 3.2, 6.4, 12.8, 19.2, 25.6, 32, 51.2 and 64 $\text{MeV}\text{nucleon}$, above the Coulomb barrier, in the time-dependent Hartree-Fock approximation. Direct and exchange Coulomb forces as well as spin-orbit forces are included. A large deformed harmonic oscillator basis is used. Spatial density and current distributions at various times are shown. The outgoing energy is found to be E₀ = 0.8E_in?28 (MeV), in the c.m. system. Fusion and fully relaxed scattering are observed at low energy. Some compression is seen at higher energies but no shock waves can be detected. Consequences for heavy-ion reactions are discussed.     

C24N24负载Sc单原子催化剂催化甲烷氧化为甲醇的理论计算

甲醇是一种很有前途的清洁能源,有望替代不可再生的石油能源.因此,将储量巨大,但不易运输的甲烷氧化为甲醇具有十分重要的意义.首先通过密度泛函理论(density functional theory, DFT)计算研究了Sc原子与C₂₄N₂₄之间的稳定性.结果表明,Sc原子与C₂₄N₂₄的结合能(-9.064 eV)小于Sc原子的内聚能(-4.518 eV),即Sc@C₂₄N₂₄具有良好的稳定性.在此基础上,进一步研究了甲烷在Sc@C₂₄N₂₄表面催化氧化制备甲醇的工艺过程,以N₂O为氧化剂在Sc@C₂₄N₂₄单原子上进行甲醇的催化氧化反应.结果表明：N₂O首先吸附在Sc@C₂₄N₂₄上,然后直接分解为N₂和O_ads.N₂...     

B/N掺杂对于石墨烯纳米片电子输运的影响

选用锯齿(zigzag)型石墨烯纳米片为研究对象, Au作为电极, 分子平面与Au的(111)面垂直, 并通过末端S原子化学吸附于金属表面, 构成两种分子器件: 一种是在纳米片的边缘掺杂N(B)原子, 发现电流-电压具有非线性行为, 但是整流系数较小, 特别是掺杂较多时, 整流具有不稳定性; 另一种是用烷链把两个石墨烯片连接, 在烷链附近和石墨烯片的边缘进行N(B)掺杂, 发现在烷链附近掺杂具有较大的整流, 但是掺杂的原子个数和位置会影响整流性能. 研究表明: 整流主要为正负电压下分子能级的移动方向和空间轨道分布不同导致. 部分体系中的负微分电阻现象主要由于偏压导致能级移动和透射峰形态的改变, 并且在某些偏压下主要透射通道被抑制而引起. 关键词： 石墨烯纳米片 电子输运 整流行为 非平衡格林函数方法     

L12型铝合金的结构、弹性和电子性质的第一性原理研究

运用第一性原理方法研究了L12型铝合金相Al3Sc和Al3Zr的晶体结构、电子结构和弹性.结合能和形成能的计算表明,两种合金具有较强的合金化能力,且Al3Zr较Al3Sc具有更强的结构稳定性.电子结构分析表明,费米能级以下较多的价电子数决定了Al3Zr具有较强的结构稳定性.计算并分析比较了两种合金相的单晶弹性常数(C11,C12和C44)以及多晶弹性模量(体弹性模量B、剪切模量G、杨氏模量Y、泊松比ν和各向异性因子A).通过对比实验和其他理论计算结果,进一步分析和解释了两种合金相的力学性质.     

Interaction of different types of nanocages (Al12N12, Al12P12, B12N12, Be12O12, Mg12O12, Si12C12 and C24) with HCN and ClCN: DFT,TD-DFT,QTAIM, and NBO calculations

In this work, the ability of different types of nanocages including Al₁₂N₁₂, Al₁₂P₁₂, Be₁₂O₁₂, B₁₂N₁₂, Si₁₂C₁₂, Mg₁₂O₁₂ and C₂₄ for the adsorption and detection of poisonous gases HCN and ClCN has been investigated, theoretically using the D3 dispersion corrected density functional theory (DFT-D3). The absorption spectra of HCN–nanocage and ClCN–nanocage complexes were calculated by the time-dependent density functional theory (TD-DFT) and compared with the calculated absorption spectrum of isolated nanocage to investigate the ability of nanocage for sensing of HCN and ClCN gases. It was found that the strongest interaction between HCN (ClCN) molecule and nanocage takes place when the molecule is adsorbed via its N atom on the surface of nanocage except for C₂₄. Also, it was shown that the Al₁₂N₁₂ is the best adsorbent for HCN and ClCN gases among the selected nanocages and Si₁₂C₁₂ is the best sensor for the detection of these gases using the electroconductivity and absorption spectroscopy techniques.     

Tailoring electronic and transport properties of edge-terminated armchair graphene by defect formation and N/B doping

First principle calculations based on Density Functional Theory and nonequilibrium Green's function methods were carried out on a p-n junction device made of armchair graphene nanoribbons (GNR), with B and N doping and with defects, to examine transport properties of these systems. Doping and defects were found to lower band gap compared to pristine GNR. N-doping leads to the smallest band gap and the highest current (17.18 μA at 0.9 V bias, −12.82 μA at −1 V bias). B-doping shows the least current. Extensive delocalisation in N-doped system suggests a strong coupling between p and n parts, making the system a high rectifying diode. Linear correspondence between transmission coefficient and projected density of states suggest robust negative differential resistance effect. Tuning of efficiency of such p-n junction by doping and defect suggests the design of suitable nanoelectronic devices in future.