有机分子吸附和衬底调控锗烯的电子结构

锗基集成电子学的发展潜力源于其极高的载流子迁移率以及与现有的硅基和锗基半导体工业的兼容性,而锗烯微小带隙能带特点极大程度地阻碍其应用.因此,在不降低载流子迁移率的情况下,打开一个相当大的带隙是其应用于逻辑电路中首先要解决的问题.本文采用范德瓦耳斯力修正的密度泛函理论计算方法,研究了电场作用下有机分子吸附和衬底对锗烯原子结构和电学性质的影响.研究结果表明,有机分子吸附和衬底通过弱相互作用破坏了锗烯亚晶格的对称性,从而在狄拉克点上打开了相当大的带隙.苯/锗烯和六氟苯/锗烯体系均在K点打开了带隙.当使用表面完全氢化的锗烯(锗烷HGeH)衬底时,苯/锗烯/HGeH和六氟苯/锗烯/HGeH体系的带隙可进一步变宽,带隙值分别为0.152和0.105 eV.在外电场作用下,上述锗烯体系可实现大范围的近似线性可调谐带隙.更重要的是,载流子迁移率在很大程度上得以保留.本文提出了一种有效的可调控锗烯带隙的设计方法,为锗烯在场效应管和其他纳米电子学器件中的应用提供了重要的理论指导.     

锗烷（GeH4）的高压超导相

通过从头算演化理论的结构预测方法,文章作者提出了GeH4的一个高压金属相结构（单斜C2/c）.这一结构包含奇特的“H2” 单元. 焓的计算结果表明,GeH4 在压力低于196 GPa时分解为单质Ge 和H2, 而在高于这一压力时C2/c结构稳定存在.在220 GPa压力下, 线性响应微扰理论的计算结果表明,C2/c结构的电子-声子相互作用参数为1.12, 其超导转变温度达到64 K.     

锗烷(GeH4)的高压超导相

通过从头算演化理论的结构预测方法,文章作者提出了GeH4的一个高压金属相结构(单斜C2/c),这一结构包含奇特的"H2"单元.焓的计算结果表明,GeH4在压力低于196 GPa时分解为单质Ge和H2,而在高于这一压力时C2/c结构稳定存在.在220 GPa压力下,线性响应微扰理论的计算结果表明,C2/c结构的电子一声子相互作用参数为1.12,其超导转变温度达到64 K.     

氢空位簇调控锗烷的电子结构和分子掺杂

锗烷因其合适的带隙、较高的电子迁移速率、较好的环境稳定性、较小的电噪声和超薄的几何结构,有望取代现有硅基或锗基材料成为下一代半导体器件的理想载体.基于密度泛函理论和非平衡格林函数的第一性原理方法,研究了不同构型和浓度的氢空位簇对锗烷电子结构及锗烷中四硫富瓦烯(tetrathiafulvalene,TTF)分子掺杂性能的影响.计算结果表明,不同构型氢空位簇的引入可诱导Germanane Dehydrogenated-x H (G_D–xH)体系产生不同性质的磁性,且磁矩大小亦与Lieb定理的预测结果相符,并能在GD-x H (x=1, 4, 6)体系自旋向下的能带结构中实现由缺陷态引起的类p型半导体掺杂效应,其电子激发所需的能量则会随着体系脱氢浓度的升高而不断降低.吸附TTF分子后, G/TTF和G_D-xH/TTF (x=1, 2, 6)体系表现出分子掺杂效应,且GD-x H/TTF (x=1, 6)体系因分子轨道与缺陷态的杂化作用,可在自旋向上与自旋向下的能带结构中形成不同的掺杂类型.进一步的量子输运计算还表明, Armchair和Zigzag...     

GaAs(111)表面硅烯、锗烯的几何及电子性质研究

基于密度泛函理论的第一性原理计算方法, 系统研究了硅烯、锗烯在GaAs(111) 表面的几何及电子结构. 研究发现, 硅烯、锗烯均可在As-中断和Ga-中断的GaAs(111) 表面稳定存在, 并呈现蜂窝状六角几何构型. 形成能计算结果证明了其实验制备的可行性. 同时发现硅烯、锗烯与GaAs表面存在共价键作用, 这破坏了其Dirac电子性质. 进一步探索了利用氢插层恢复硅烯、锗烯Dirac电子性质的方法. 发现该方法可使As-中断面上硅烯、锗烯的Dirac电子性质得到很好恢复, 而在Ga-中断面上的效果不够理想. 此外, 基于原子轨道成键和杂化理论揭示了GaAs表面硅烯、锗烯能带变化的物理机理. 研究结果为硅烯、锗烯在半导体基底上的制备及应用奠定了理论基础.     

锗烯在金属衬底上的结构及电子性质的第一性原理研究

基于密度泛函理论的第一性原理计算,我们系统的研究了锗烯在Pt(111)、Au(111)和Al(111)表面的几何和电子结构.在这三种金属衬底上寻找到了9种结构,其中Al(111)-a、Au(111)-b和Pt(111)-c结构就是目前实验上已经成功制备的结构.我们还发现了其余6种目前理论和实验均没有提出,此外,Al(111)-b、Au(111)-a和Pt(111)-b结构的Dirac态仍保留,这些结构的形成能均大于范德瓦尔斯作用,因此非常有希望在实验上制备出来,应用于量子自旋霍尔效应的研究.本文的研究为锗烯在半导体衬底上的制备及应用奠定了理论基础.     

氢分子间色散相互作用能的自然轨道泛函

理论上对分子间色散相互作用能的精确计算一直是个难点问题.密度矩阵泛函基于非定域量一阶密度矩阵为基本变量,它与色散相互作用起源于电子间的非定域关联特性相吻合.论文以最简单的氢分子为研究对象,通过分析两相互平行的氢分子间色散相互作用能,构造出了该体系中色散相互作用能的自然轨道泛函.结果表明:描述该体系中色散相互作用能的自然轨道泛函形式为包含有4个轨道的非交换和库伦积分.该结果对发展色散相互作用能的密度矩阵泛函理论具有重要的参考价值.     

层数调控磷烯能带与光学性质的研究

近年来,黑磷作为兼具石墨烯和过渡金属硫化物之长的新型二维材料而倍受关注.本文基于密度泛函理论,研究了不同厚度黑磷的电子结构与光学性质.结果表明,黑磷的性质与其厚度密切相关,可通过厚度调整实现能带与光学性质的可调控性.层间相互作用导致费米能级附近价带和导带的劈裂,是造成黑磷带隙随层数减小的根本原因.黒磷的静态折射率和静态反射率的大小均随层数的增大有增大的趋势,并且各层黑磷的反射峰均位于紫外光波段.黑磷对光的吸收涵盖了可见光到紫外光区域,对光的损失范围小于4eV.本文基于能带图和分波态密度图,从电子跃迁的角度分析了黑磷各项光学性质的变化情况,旨在为黑磷的带隙及光学性质层数可调控性提供理论依据.     

Na-呋喃荷移络合物弱相互作用的密度泛函理论研究

在B3LYP／6－311＋G*水平上,对Na-呋喃体系可能存在的弱相互作用复合物进行了全自由度能量梯度优化,发现了Na-呋喃体系存在两个能量极小结构A、B,其中,结构A是Na原子的3s^1电子直接和呋喃杂环体系中的所有重原子的共轭大π 体系 相互偶合,形成一个具有Cs对称性的金属有机复合物;而结构B为Na 原子的3s^1电子主要通过杂原子O和杂环上原有的五中心六电子大π体系形成一个新的平面六中心七电子大π体系,具有C2V对称 性。结果B较结构 A 稳定3.40kJ/mol。结构A中的Na-O键长为0.38nm,<COC为106.9°,由于金属Na对呋喃杂环的作用使整个分子平面变形,C1、C2、C3、C4在同一个平面内,而05则稍微翘离平面且05原子距离由C1、C2、C3、C4 组成的平面的垂直距离约为0.035nm.结构B中Na-O键长为0.26nm,＜COC为106.8°。金属Na原子和杂环中所有的原子在同一个平面内。并在MP2和B3LYP水平下,用3－311＋G＊基组精确计算了最稳定结构B的结合能为△E＝4.5-5.1kJ/mol.     

锗烯与异氰酸多通道反应的理论计算

采用密度泛函理论B3LYP方法研究了单重态GeH₂与HNCO的反应机理.在B3LYP/6-311++G**水平上对反应物、中间体、过渡态进行了全几何参数优化,通过频率分析和内禀反应坐标（IRC）确定中间体和过渡态,用QCISD（T）/6-311++G**方法计算了各个驻点的单点能.计算表明单重态的锗烯与异氰酸的反应有抽提氧、插入N-H键、抽提亚氨基的反应路径.采用经Winger校正的Eyring过渡态理论分别计算了1个大气压、不同温度下反应势垒较低通道的热力学及动力学性质,结果表明插入N-H键反应（GeH₂+HNCO→IM7→TS6→P2）通道在温度400 K～1400 K内,有较高的平衡常数和反应速率常数,为主反应通道,主产物为GeH₃NCO.     

Current developments in silicene and germanene

Exploration of the unusual properties of the two‐dimensional materials silicene and germanene is a very active research field in recent years. This paper therefore reviews the latest developments, focusing both on the fundamental materials properties and on possible applications. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Topological phases of silicene and germanene in an external magnetic field: Quantitative results

We investigate the topological phases of silicene and germanene that arise due to the strong spin–orbit interaction in an external perpendicular magnetic field. Below and above a critical field of 10 T, respectively, we demonstrate for silicene under 3% tensile strain quantum spin Hall and quantum anomalous Hall phases. Not far above the critical field, and therefore in the experimentally accessible regime, we obtain an energy gap in the meV range, which shows that the quantum anomalous Hall phase can be realized experimentally in silicene, in contrast to graphene (tiny energy gap) and germanene (enormous field required). (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Dispersion interactions in density‐functional theory

Density‐functional theory (DFT) allows for the calculation of many chemical properties with relative ease, thus making it extremely useful for the physical organic chemistry community to understand and focus on various experiments. However, density‐functional techniques have their limitations, including the ability to satisfactorily describe dispersion interactions. Given the ubiquitous nature of dispersion in chemical and biological systems, this is not a trivial matter. Recent advances in the development of DFT methods can treat dispersion. These include dispersion‐corrected DFT (using explicit, attractive dispersion terms), parameterized functionals, and dispersion‐correcting potentials, all of which can dramatically improve performance for dispersion‐bound species. In this perspective, we highlight the achievements made in modeling dispersion using DFT. We hope that this will provide valuable insight to both computational chemists and experimentalists, who aim to study physical processes driven by dispersion interactions. Copyright © 2009 John Wiley & Sons, Ltd.     

Ab initio interatomic potentials for low-energy He ion/atom scattering

Ab initio (density functional theory) binary interatomic potentials have been calculated for low-energy He projectile interactions with target atoms having atomic numbers (Z ₂) from 6 to 54 (C to Xe). The calculated potentials cover the energy range that is typical for low-energy ion He ion/atom-scattering spectroscopy (≤2–7 keV, depending on Z ₂). For constant R, the screening function exhibits Z ₂ oscillations that are indicative of the electronic stabilities of the corresponding quasi-molecules; screening function minima are observed for the quasi-molecules that are isoelectronic with the noble gases. The He–Z ₂ interatomic potentials calculated for target elements lighter than Rb are suitable for use in simulations of low-energy ion-scattering experiments. However, the potentials calculated for target atoms heavier than Kr do not offer any clear benefits over the existing empirical potentials. The solid-state potential shift applicable to scattering in metallic solids has been estimated as typically 0 to+10 eV, using a simple thermodynamic model that exploits the similarities between the valence states of an He–Z ₂ quasi-molecule and the corresponding united atom.     

DFT study of dihydrogen interactions with lithium containing organic complexes C4H4-mLim and C5H5-mLim （m = 1, 2）

The interactions of dihydrogen with lithium containing organic complexes C₄H_4-mLi_m and C₅H_5-mLi_m (m = 1, 2) were studied by means of density functional theory (DFT) calculation. For all the complexes considered, each bonded lithium atom can adsorb up to five H₂ molecules with the mean binding energy of 0.59 eV/H₂ molecule. The interactions can be attributed to the charge transfer from the H₂ bonding orbitals to the Li 2s orbitals. The kinetic stability of these hydrogen-covered organolithium molecules is discussed in terms of the energy gap between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO). The results indicate that these organiclithium structures can perhaps be used as building units for potential hydrogen storage materials.     

Some Remarks on the Final State Interactions in B → πK Decays

Careful discussions are made on some points wfiich are met in studying B-decay final state interactions, taking the B⁰ → π + K^- process as an example. We point out that π-exchange rescatterings are not important, whereas for D^* and D^** exchanges, since the B₀ → D+D_s^-, decay has a large branching ratio their contributions may be large enough to enhance the B → πK branching ratio significantly. However our estimates fail to predict a large enhancement.     

Localization of π‐electron density in twisted bilayer graphene

In bilayer graphene, mutual rotation of layers has strong effect on the electronic structure. We theoretically study the distribution of electron density in twisted bilayer graphene with the rotation angle of 21.8° and find that regions with AA‐like and AB‐like stacking patterns separately contribute to the interlayer low‐energy van Hove singularities. In order to investigate the peculiarities of interlayer coupling, the charge density map between the layers is examined. The presented results reveal localization of π‐electrons between carbon atoms belonging to different graphene layers when they have AA‐like stacking environment, while the interlayer coupling is stronger within AB‐stacked regions.

Charge density map for bilayer graphene with a layer twist of 21.8° (interlayer region).     

The Influence of Spin-Orbit Interaction on the Electron-Phonon Coupling in Tl-Rich Cubic AuCu3-Type Superconductors: Comparison with La3Tl

In this work, the role of spin-orbit coupling (SOC) in ATl₃ (A = Ca, Y, La, and Th) and La₃Tl is investigated by theoretical investigation of their structural, electronic, elastic, mechanical, phonon, and electron–phonon interaction properties. The effect of SOC on the electronic band structures of these compounds is that some of the degeneracies at the high symmetry points that would exist in a scalar relativistic calculation without SOC are removed by considering this coupling. The replacement of La and Tl atoms in LaTl₃ increases the value of the density of states at the Fermi level N($E_{\mathrm{F}}$) by a factor of 2.1. Furthermore, this replacement makes almost all phonon modes in La₃Tl softer than those in LaTl₃. Both softer phonon modes and higher N($E_{\mathrm{F}}$) make the electron–phonon interaction in La₃Tl much stronger than in LaTl₃. The presence of SOC increases the $T_{\mathrm{c}}$ values of LaTl₃ by 34% (from 1.151 to 1.542 K) and of ThTl₃ by 65% (from 0.479 to 0.793 K), resulting in good agreement with the corresponding experimental values of 1.63 and 0.87 K. The inclusion of SOC also improves the agreement with the experiment for $T_{\mathrm{c}}$ values of CaTl₃, YTl₃, and La₃Tl.     

The study on interactions between 1‐ethyl‐3‐methylimidazolium chloride and benzene/pyridine /pyrrole/thiophene

The density functional theory was used to investigate the interactions between 1‐ethyl‐3‐methylimidazolium chloride ([EMIM]Cl) and benzene/pyridine/pyrrole/thiophene. The complexes formed between [EMIM]Cl and benzene/pyridine/pyrrole/thiophene were optimized at the ωB97XD/6‐31++G** level, and the optimized complexes were further analyzed by natural bond orbital, atoms in molecules, and noncovalent interaction. The calculated results show that the interaction energy between ionic liquid and benzene/pyridine/pyrrole/thiophene is in the order pyrrole > pyridine > thiophene > benzene. The major interactions between ionic liquid and benzene/pyridine/pyrrole/thiophene are hydrogen bonding and π‐π interaction, accompanied by C···H, N···H, H···H, and S···H weak interactions. Both cation and anion of ionic liquid are involved in interactions with aromatic compounds.     

β石墨炔衍生物结构稳定性及电子结构的密度泛函理论研究

石墨炔衍生物比石墨烯具有更多样化的原子结构,因而具有潜在的更丰富的电子结构.通过第一性原理密度泛函理论研究方法系统研究了β石墨炔衍生物的结构稳定性、原子构型和电子结构.本文计算的β石墨炔衍生物系列体系由六边形碳环(各边原子数N=1—10)通过顶点相连而成.对结构与能量的计算分析表明:当N为偶数时,β石墨炔拥有单、三键交替的C—C键结构,其能量比N为奇数时,拥有连续C=C双键的石墨炔衍生物更稳定.计算的能带结构和态密度显示:根据碳环各边原子个数N的奇偶性不同,β石墨炔可呈现金属性(N为奇数时)或半导体特性(N为偶数时).该奇偶依赖的原子构型和电学性质是由Jahn-Teller畸变效应导致,与碳环各边原子碳链的实际长度无关.计算发现部分半导体β石墨炔(N=2,6,10)呈现狄拉克锥能带特征,其带隙约10 meV,且具有0.255×10~6—0.414×10~6m/s的高电子速度,约为石墨烯电子速度的30%—50%.本密度泛函理论研究表明,将sp杂化碳原子引入石墨烯六边形碳环的边上,可通过控制六边形各边原子个数的奇偶性调制其金属和半导体电子特性或狄拉克锥的形成,为免掺杂和缺陷调控纳米碳材料的电学性质和设计碳基纳米电子器件提供了理论依据.