掺杂硅烯吸附CO分子的第一性原理研究

硅烯具有独特的电子、光学、热学、力学以及量子特性,在电子器件、电极材料、储氢材料、催化剂和气体传感器等领域有巨大的潜在应用价值.本文采用基于密度泛函理论的第一性原理计算方法,利用Materials Studio软件中的CASTEP程序包对硅烯与CO分子之间的吸附行为进行了研究.重点研究了硅烯掺杂方式、CO分子吸附构型及硅烯空位缺陷浓度对CO分子吸附的影响,研究结果表明：1)空位缺陷硅烯对CO分子的吸附能力最强;2)碳原子垂直朝向空位缺陷硅烯更有利于CO分子的吸附;3)硅烯对CO分子的吸附能力随其空位浓度的增加显著增强;4)空位硅烯向CO分子转移电荷,电荷转移量与二者的吸附作用强弱呈正相关.该研究可为硅烯基CO气体传感器的设计提供理论指导.     

Mg-F受主-施主共掺SnO_2的第一性原理研究

利用基于密度泛函理论(DFT)的第一性原理平面波赝势法,研究了Mg-F受主-施主共掺杂SnO_2的结构稳定性、能带结构、态密度及布居分布.结果表明,Mg-F掺杂能形成稳定的掺杂体系,在价带顶附近F 2p的态密度峰值强度较大,Mg-F原子之间杂化强,引入施主掺杂元素F有利于Mg受主掺杂的稳定性,同时Mg-O之间电子重叠布居值增大,原子之间的重叠增加,共有化增强,可使导电性能进一步提升.     

第一性原理计算：锰酸锂掺杂Fe和Co的性质研究

文章基于密度泛函理论的第一性原理计算,研究了LiMn2O4电池材料在掺杂Fe和Co离子时的电子结构和电化学性能。发现Fe\Co取代Mn3+在热力学上是会更加稳定,提升电化学性能。掺杂Fe后,LiMn2O4电池材料晶格参数减小(约0.3%);掺杂Co后,LiMn2O4电池材料晶格参数减小(约0.5%)。这两种掺杂方式让与之相邻的Mn3+被氧化成Mn4+,从而降低了Jahn-Teller畸变情况产生可能性。对于掺Fe尖晶石型锰酸锂(Li8Mn15FeO32),Mn环境中的Li离子会更容易被提取,第一次放电电压从原来的3.7V增加至4.623V;对于掺Co尖晶石型锰酸锂(Li8Mn15CoO32),第一次放电电压从原来的3.7V增加至4.101V。研究为锂电池电容量研究提供理论数据的参考。     

First-principles study of martensitic phase transformation of TiRh alloy

Geometric structures and atomic positions were studied with plane wave pseudo-potential method based on density functional theory for cubic, tetragonal, and monoclinic phases of TiRh alloy. Their phonon dispersion curves were obtained with frozen phonon method at harmonic approximation using density-functional perturbation theory. Our calculations revealed that both B2 and L1₀ phases are thermodynamically unstable. Jahn-Teller effect triggers the occurrence of Bain transformation from cubic to tetragonal phase, and then soft-mode phonon further leads to the transition from tetragonal to monoclinic phase on cooling. The monoclinic phase was predicted to be P2/m space group through atomic vibrational movement along [001] direction of virtual frequency modes of L1₀ phase. The temperature from B2 to L1₀ and then to P2/m were predicted to be about T=1100.53 K and T=324.48 K through free energy calculations with the electronic plus vibrational energy of formation, respectively, which is in good agreement with experimental observations.     

Passivated B-O,B-S codoping to improve the photocatalytic efficiency in C2N monolayer: First-principles study

In this paper, we explored systematically the effects of non-metal elements (B, O, and S) monodoping and passivated codoping of B-S and B-O in C₂N monolayer. The band structure, band edge position and charge density distribution of doped-C₂N are investigated. Our results show that the monodoping of B, O, S introduce flat impurity bands around the Fermi level. The passivated codoping of B-O or B-S can effectively decrease the bandgap, and the band edge position is more favorable for water splitting compared with that of C₂N monolayer. A large dispersion of conduction and valance band can be observed for B-S or B-O codoping, which is beneficial for the carriers' mobility. Moreover, the separation of electron and hole density to extend after doping can decrease the combination rate in photocatalytic. Our results predict that passivated B-S or B-O doped C₂N are promising water-splitting photocatalyst.     

石墨烯纳米片电子结构和量子输运特性第一原理研究

用基于密度泛函理论的原子紧束缚方法计算研究单层石墨烯纳米圆片和纳米带的电子结构,并结合第一原理和非平衡函数法计算量子输运特性.通过电子能态和轨道密度分布研究纳米碳原子层的电子成键状态,结合电子透射谱、电导和电子势分布分析电子散射与输运机制.石墨烯纳米带和纳米圆片分别呈现金属和半导体的能带特征,片层边缘上电极化分别沿垂直和切向方向,电子电导出现较大的差异,来源于石墨烯纳米圆片边缘的突出碳原子环对电子的强散射.石墨烯纳米带的电子透射谱表现为近似台阶式变化并在费米能级处存在弹道电导峰,而石墨烯纳米圆片的电子能带和透射谱在费米能级处开口并且因量子限制作用呈现更加离散的多条高态密度窄能带和尖锐谱峰.     

The influence of nitrogen vacancies on the magnetic and electronic properties of ruthenium mononitride: First-principles study

We present FLAPW-GGA calculations of the magnetic and electronic properties of cubic RuN_x (x=1.0, 0.75 and 0.50). We find that RuN exhibits a ferromagnetic ground state and the local ruthenium magnetic moment abruptly decreases with nitrogen vacancies. The relative positions of t_2g and e_g states and the Ru 4d–N 2p hybridization in RuN_x are discussed. We have also found that the magnetic behavior for RuN_x vs. FeN_x as dependent on the nitrogen vacancies content displays an opposite trend.     

第一性原理研究half-Heusler合金CoVTe和FeVTe半金属性及磁性的稳定性

本文构建了half-Heusler合金CoVTe和FeVTe.运用基于第一性原理的全势能线性缀加平面波方法,计算half-Heusler合金CoVTe和FeVTe的电子结构.电子结构的自旋极化计算结果表明,合金CoVTe和FeVTe具有半金属性,它们的半金属隙分别为0.21 eV和0.20 eV.磁性计算结果显示,合金CoVTe和FeVTe的晶胞总磁矩分别为2.00μ_B和1.00μ_B;合金晶胞中过渡金属V具有较强的原子磁矩,Te的原子磁矩较弱,而且为负值.使合金晶格均匀形变△a/a_0在±7%的范围内变化,分别计算CoVTe和FeVTe的电子结构.计算结果表明,晶格均匀形变△a/a_0分别为-7%—+7%和-4.8%—+7%时,合金CoVTe和FeVTe仍然保持半金属性,并且晶胞总磁矩分别稳定于2.00μ_B和1.00μ_B.     

Structural and electronic properties of copper nanowire encapsulated into BeO nanotube: First-principles study

We present a systematic study on the structural and electronic properties of close-packed Cu nanowires encapsulated in a series of zigzag (n,0) BeONTs using first-principles calculations. The initial shapes (cylindrical CuNWs and BeONTs) are preserved without any visible changes for the Cu_m@(n,0) (m=6 or 8, 8≤n≤14) combined systems. The most stable combined systems are Cu₆@(10,0) and Cu₈@(11,0) with an optimal tube-wire distance of about 2.8 Å and a simple superposition of the band structures of their components near the Fermi level. A quantum conductance of 3G₀ is obtained for both Cu₆ and Cu₈ nanowires in either free-standing state or filled into BeONTs. The electron transport will occur only through the inner CuNW and the inert outer BeONT serves well as insulating cable sheath. So the Cu₆@(10,0) and Cu₈@(11,0) combined systems is top-priority in the ULSI circuits and MEMS devices that demand steady transport of electrons.     

First-principles study on structural and electronic properties of copper nanowire encapsulated into GaN nanotube

We present a systemic study of the structural and electronic properties of Cu_n nanowires (n=5, 9 and 13) encapsulated in armchair (8,8) gallium nitride nanotubes (GaNNTs) using the first-principles calculations. We find that the formation processes of these systems are all exothermic. The initial shapes are preserved without any visible changes for the Cu₅@(8,8) and Cu₉@(8,8) combined systems, but a quadratic-like cross-section shape is formed for the outer nanotube of the Cu₁₃@(8,8) combined system due to the stronger attraction between nanowire and nanotube. The electrons of Ga and N atoms in outer GaN sheath affect the electron conductance of the encapsulated metallic nanowire in the Cu₁₃@(8,8) combined system. But in the Cu₅@(8,8) and Cu₉@(8,8) combined systems, the conduction electrons are distributed only on the copper atoms, so charge transport will occur only in the inner copper nanowire, which is effectively insulated by the outer GaN nanotube. Considering the maximal metal filling ratio in nanotube, we know that the Cu₉@(8,8) combined system is top-priority in the ultra-large-scale integration (ULSI) circuits and micro-electromechanical systems (MEMS) devices that demand steady transport of electrons.     

Magnetic and optical properties of Cu-doped ZnO nanosheet: First-principles calculations

We performed first-principles calculations within density-functional theory to study the magnetic and optical properties of Cu-doped ZnO nanosheet (NS). We found that Cu atom prefers to substitute for Zn site and can induce a local magnetic moment of 1.00 μ_B per unit in ZnO NS. When two Zn atoms are substituted by two Cu dopants, they tend to form a cluster and ferromagnetic (FM) ordering becomes energetically more favorable. In addition, localized states appear within the band gap due to the introduction of Cu dopant to ZnO NS. With increasing Cu concentrations, both the imaginary part of dielectric function and the absorption spectrum exhibit a red-shift behavior, which are in good agreement with the recent experimental results. The ferromagnetic coupling can be attributed to the p–d hybridization mechanism. The intriguing properties of Cu-doped ZnO NS may be promising for designing novel multifunctional nanodevice.     

Fe掺杂碳纳米管吸附甲硝唑的第一性原理计算

甲硝唑(MNZ)的滥用对水环境造成了严重的污染.本文采用第一性原理计算的方法,研究了单壁碳纳米管(CNT)和Fe掺杂碳纳米管(Fe-CNT)对MNZ的吸附作用.分别计算了单壁CNT和Fe-CNT与MNZ的吸附结构、吸附能、电子轨道、电荷转移、态密度等.结果表明原始CNT对MNZ吸附作用较弱,而Fe-CNT与MNZ的相互作用明显增强.因此,Fe-CNT有望成为吸附水中污染物MNZ的候选材料.     

First-principles calculations for anisotropy of iron-based superconductors

We perform first-principles calculations for anisotropy of various iron-based superconductors. The anisotropy ratio γ_λ of the c-axis penetration depth to the ab-plane one is relatively small in BaFe₂As₂, LiFeAs and FeSe, indicating that the transport applications are promising in these superconductors. On the other hand, in those having perovskite-type blocking layers such as Sr₂ScFePO₃ we find a very large value, γ_λ ? 200, comparable to that in strongly anisotropic high-T_c cuprate Bi₂Sr₂CaCu₂O_8−δ. Thus, the intrinsic Josephson junction stacks are expected to be formed along the c-axis, and novel Josephson effects due to the multi-gap nature are also suggested in these superconductors. We also examine the doping effect on the anisotropy of LaFeAsO.     

Structural,electronic properties and stability of Ag-doped GaAs nanowires: First-principles study

First-principles computations have been addressed to determine the effects of Ag substitution to the structural, electronic properties and stability of Ag-doped GaAs NW. Our results show that the substitutional Ag energetically prefers to substitute the surface Ga (E_f=−0.529 eV) under As-rich conditions and introduces a much shallow (0.19 eV above the Fermi) acceptor level, which is of typical p-type behavior. With the increase in the Ag concentration, the p-type character gradually weakens and n-type character arises. Thus, one can expect to synthesize Ag-doped GaAs NWs for p-type or n-type applications with the control of Ag concentration and its microarrangement.     

First-principles study on ferromagnetism in C-doped AlN

First-principles calculations are performed to study the electronic structures and magnetic properties of C-doped AlN. Both generalized gradient approximation (GGA) and GGA+U calculations show that a substitutional C atom introduces magnetic moment of about 1.0 μB, which comes from the partially occupied 2p orbitals of the C, its first neighboring Al and first neighboring N atoms (GGA) or out-of-plane first and fifth neighboring N atoms (GGA+U), among which the atomic moment of the C is the biggest. The U correction for the anion-2p states obviously changes the magnetic moment distribution of Al and N atoms and transforms the ground state of C-doped AlN to insulating from half-metallic. The C atoms can induce ferromagnetic ground state with long-range couplings between the moments in C-doped AlN. The ferromagnetic coupling can be explained in terms of the two band coupling model.     

First-principles study on the Ni@Pt12 Ih core-shell nanoparticles: A good catalyst for oxygen reduction reaction

The adsorption, diffusion and dissociation properties of O₂ on the icosahedron (Ih) Ni@Pt12 core-shell nanoparticle were investigated using the ab initio density functional theory calculations. It is found that, compared with the Pt(111) surface, the Ih Ni@Pt12 core-shell nanoparticle can enhance the adsorption, diffusion and dissociation of O₂, as well as the adsorption and diffusion of the atomic O (the dissociation product of O₂), and therefore serve as a good catalyst for oxygen reduction reaction. Our study gives a reasonable theoretical explanation to the high catalytic activity of the Ni@Pt core-shell nanoparticles for the oxygen reduction reaction.     

First-principles studies of Fe atoms adsorption on hydrogen-terminated boron nitride nanoribbons

By using density functional theory (DFT), we have studied the adsorption of Fe atoms on boron nitride nanoribbons (BNNRs). The stabilities of Fe atoms adsorption on BNNRs for the inner sites are very weakly dependent on the adsorption sites and Fe atoms energetically prefer to be adsorbed on the edge boron sites. The analysis of electronic structures shows that the most of the stable systems are the interesting spin gapless semiconductors. The magnetism of the Fe adatom is preserved well on the BNNRs, very close to that of the corresponding isolated atom for all the considered adsorption sites.     

First-principles study on Sb-doped SnS2 as a low cost and non-toxic absorber for intermediate band solar cell

Tin disulfide has attracted much attention on solar cell study due to its excellent optoelectronic properties in addition to just containing low-cost and non-toxic elements. Based on the HSE06-hybrid function calculations combined with Grimme's dispersion-correction method, a half-filled and delocalized intermediate band(IB) is presented in the main band gap of SnS₂ after partially Sb substituting on Sn site, which is made of the antibonding states of Sb-s and S-p states. Three-photon absorption can be realized in the doped sample and its corresponding absorption coefficient is enhanced at the visible light region thanks to the isolated and half-filled IB above the original valence band. Furthermore, Sb_Sn always has the lowest formation energy than other Sb-related defects (i.e. Sb_S and Sb_i) based on the defect formation energy calculations. Therefore, Sb-doped SnS₂ is suggested as a promising candidate for the absorber of intermediate band solar cell.     

高温高压下碳化钨晶体的结构、力学、电子、光学以及热力学性能的第一性原理计算

本文利用密度泛函理论中的广义梯度近似对碳化钨晶体的三种结构(碳化钨相、闪锌矿相以及纤锌矿相)进行了优化,得到能量最低的稳定构型,并在此基础上计算了它的力学、电子、光学和高温高压下的热力学性质.研究表明:在0～300 GPa压力范围内,碳化钨相具有最高的稳定性.同时,高压下碳化钨相的弹性常数满足Born-Huang准则,且0 GPa和300 GPa下的声子色散没有虚频,证明了高压下碳化钨相的静力学稳定性和动力学稳定性.电子性质表明了碳化钨的金属性.光学性质表明碳化钨在高能区很难吸收光.热力学性质的研究表明:体积比V/V_0对压强的变化更敏感;高温时C_V曲线近似一条直线;给定压强下热膨胀系数α在600 K温度以上增长非常缓慢;压强对德拜温度Θ_D的影响较大;在低压下格林艾森系数γ的变化较大.