Ab initio nonadiabatic molecular dynamics study on spin–orbit coupling induced spin dynamics in ferromagnetic metals

Understanding the photoexcitation induced spin dynamics in ferromagnetic metals is important for the design of photo-controlled ultrafast spintronic device.In this work,by the ab initio nonadiabatic molecular dynamics simulation,we have studied the spin dynamics induced by spin–orbit coupling(SOC)in Co and Fe using both spin-diabatic and spin-adiabatic representations.In Co system,it is found that the Fermi surface(E_(F))is predominantly contributed by the spin-minority states.The SOC induced spin flip will occur for the photo-excited spin-majority electrons as they relax to the E_(F),and the spin-minority electrons tend to relax to the EFwith the same spin through the electron–phonon coupling(EPC).The reduction of spin-majority electrons and the increase of spin-minority electrons lead to demagnetization of Co within100 fs.By contrast,in Fe system,the E_(F) is dominated by the spin-majority states.In this case,the SOC induced spin flip occurs for the photo-excited spin-minority electrons,which leads to a magnetization enhancement.If we move the E_(F) of Fe to higher energy by 0.6eV,the E_(F) will be contributed by the spin-minority states and the demagnetization will be observed again.This work provides a new perspective for understanding the SOC induced spin dynamics mechanism in magnetic metal systems.

Surface evolution of thermoelectric material KCu_(4)Se_(3) explored by scanning tunneling microscopy

Novel two-dimensional thermoelectric materials have attracted significant attention in the field of thermoelectric due to their low lattice thermal conductivity.A comprehensive understanding of their microscopic structures is crucial for driving further the optimization of materials properties and developing novel functional materials.Here,by using in situ scanning tunneling microscopy,we report the atomic layer evolution and surface reconstruction on the cleaved thermoelectric material KCu_(4)Se_(3) for the first time.We clearly revealed each atomic layer,including the naturally cleaved K atomic layer,the intermediate Se^(2-)atomic layer,and the Se^(-)atomic layer that emerges in the thermodynamic-stable state.Departing from the maj ority of studies that predominantly concentrate on macroscopic measurements of the charge transport,our results reveal the coexistence of potassium disorder and complex reconstructed patterns of selenium,which potentially influences charge carrier and lattice dynamics.These results provide direct insight into the surface microstructures and evolution of KCu_(4)Se_(3),and shed useful light on designing functional materials with superior performance.

超宽禁带半导体NaYO_(2)的光电性质的第性原理研究

超宽禁带半导体在发展电子器件的性能方面具有巨大潜力.本文利用密度泛函理论和精确的屏蔽杂化泛函计算了两种不同相的NaYO_(2)的电子和光学性质.电子结构计算结果表明,NaYO_(2)的单斜相和三方相都表现为直接带隙,大小分别5.6 eV和5.4 eV,超越了公认的金刚石和GaN半导体材料,为半导体行业提供了一个物理上现实的材料平台.研究了NaYO_(2)两相的光学性质,发现它们在红外和可见光区都是透明的.因此,NaYO_(2)可被用作红外窗口材料.

基于深度学习方法研究分子/固体界面量子化质子耦合的电荷转移过程

【目的】理解分子与固体界面发生的超快电荷转移物理机制,对于提升太阳能电池以及光催化反应的能量转化效率起着至关重要的作用。【文献范围】在许多含有氢元素的分子/固体界面,分子会以一定结构吸附,分子中的氢会在固体表面形成氢键网络。由于氢元素具有很轻的质量,同时,它在分子中常常以质子的形式存在,因此人们常常可以在分子/固体界面观察到质子电子耦合在一起的电荷转移过程,而这类过程中质子的核量子效应(Nuclear quantum effects,NQEs)无法被忽略。最近,我们发展了结合路径积分分子动力学(Path-integral molecular dynamics,PIMD)与非绝热分子动力学(Nonadiabatic moleculardynamics,NAMD)的计算方法RP-NAMD,可以有效地研究质子电子耦合的电荷转移过程。然而,其中PIMD/RPMD的巨大计算量限制了这类方法在真实体系中的应用。【方法】在本文中,我们利用深度学习方法,大幅度减小了PIMD/RPMD的计算量,使得RP-NAMD可以应用于更大的体系,并可以用来研究更长时间尺度的动力学过程。为了验证新的方法,我们选择了甲醇/二氧化钛界面作为原型体系,并研究了核量子效应在界面质子耦合的电荷转移过程的重要作用。【结论】总之,本文基于深度学习,为大家提供了一种实用的、可以用来研究核量子效应与载流子动力学耦合效应的计算方法。

二维层状As_(2)S_(3)层间键合诱导超快激发态本征局域化

具有强激子效应的二维层状材料为研究二维极限下的激发态激子行为提供了极好的平台.虽然传统二维层状半导体(如过渡金属二硫族化物)中的激子动力学已经被广泛研究,但对具有强电子/激子-声子耦合的二维层状半导体中的激子特性和动力学知之甚少.本文通过实验和理论相结合的方法,以二维层状As_(2)S_(3)为模型,揭示了由强激子-声子相互作用驱动的本征高度局域化的激子.结果表明,As_(2)S_(3)中光激发电子/空穴电荷在~110飞秒内自发局域化,产生了较大Stokes位移和较宽的光致发光.理论计算表明层间的硫原子之间光激发形成一定的层间键,引发晶格畸变和载流子局域化.本研究为理解二维半导体中激子和晶格动力学之间复杂的相互作用提供了一个全面的物理图像,对其光电特性和应用具有重要意义.

Rh氧化物团簇向单原子的原位自适应演化

负载型金属催化剂在催化过程中通常会发生相变、烧结、表面重构和解离为单原子等变化.这样的结构演化不仅可以由温度诱导,也可以由反应产生的吸附物种诱导.然而,结构的变化对催化剂的影响存在两面性,既可能因此形成新的活性位点,也可能导致催化剂失活.因此,希望催化剂在反应中进行适应反应环境的结构演化,从而形成更高效的活性位点.结构演化的途径可以是金属物种直接在催化剂表面迁移,即固-固路径;也可以是催化剂表面原子浸出到溶液中,即固-液路径.揭示具体催化剂的演化路径,对催化剂的设计与改良有重要意义.本文通过浸渍-煅烧法将RhOx团簇负载在Al_(2)O_(3)上.然而,该催化剂在氢甲酰化初始阶段并不具备反应活性,但其在反应过程中由CO诱导,原位演化成了具备催化活性的缺陷位点与Rh单原子.活化后的催化剂在110℃,30 bar合成气的条件下,丙烯氢甲酰化的比活性达到了3.0×10^(4)mol molRh^(-1)h^(-1).通过高角环形暗场像-扫描透射电子显微镜观察了活化前后催化剂表面RhOx团簇的结构变化和Rh单原子的形成,利用X射线光电子能谱、X射线吸收精细结构谱和原位漫反射傅里叶变换红外光谱观察了催化剂价态和配位结构的变化以及CO气体处理对催化剂的直接影响,结果表明,催化过程中没有形成Rh-Rh金属键,从而避免了Rh的团聚失活;通过电子顺磁共振测试研究了催化过程中催化剂表面缺陷浓度随时间的变化.通过电感耦合等离子体-原子发射光谱验证了Al_(2)O_(3)和CeO_(2)均能吸附均相Rh物种,并引入吸附能力更强的CeO_(2)捕获氢甲酰化反应中从Rh/Al_(2)O_(3)固体进入溶液中的Rh物种,利用CO探针红外检验了Rh的配位情况,证实了Rh物种的溶解-再吸附演化过程.对Rh/Al_(2)O_(3)的热过滤实验结果表明,均相Rh物种提供了18.6%的总活性,但回收后催化剂的活性损失和Rh含量的流失远低于该数字,表明部分再吸附作用在一定程度上提高了催化剂的稳定性.结构表征和机理研究揭示了Rh物种的固-固和固-液-固两种原位演化路径.在催化过程中,RhOx团簇被CO还原形成氧缺陷,使得周围的Rh原子获得了吸附CO的能力.同时,Rh物种在反应底物和溶剂的作用下,溶解到溶液中,进而部分再吸附回到载体上.综上,本文不仅提供了一种高效的丙烯氢甲酰化催化剂,也加深了对催化剂动态演化的认识.

Effects of atomic corrugations on electronic structures in Pb_(1-x)Bi_(x) thin films

We carried out experimental investigations of the geometric effect on the electronic behavior in Pb_(1-x)Bi_(x) thin films by scanning tunneling microscopy and spectroscopy.Single crystal monolayer Pb_(0.74)Bi_(0.26) and two-monolayer Pb_(0.75)Bi_(0.25)Pb_(1-x)Bi_(x) thin films were fabricated by molecular beam epitaxy,where large surface corrugations were observed.Combined with tunneling spectroscopic measurements,it is found that atomic corrugations can widely change the electronic behaviors.These findings show that the Pb_(1-x)Bi_(x) system can be a promising platform to further explore geometry-decorated electronic behavior in two-dimensional metallic thin films.

Resonant Charge Transport Assisted by the Molecular Vibration in Single-Molecule Junction from Time-Domain ab initio Nonadiabatic Molecular Dynamics Simulations

Using ab initio nonadiabatic molecular dynamics simulation, we study the time-dependent charge transport dynamics in a single-molecule junction formed by gold(Au) electrodes and a single benzene-1,4-dithiol(BDT)molecule. Two different types of charge transport channels are found in the simulation. One is the routine nonresonant charge transfer path, which occurs in several picoseconds. The other is activated when the electronic state of the electrodes and that of the molecule get close in energy, which is referred to as the resonant charge transport. More strikingly, the resonant charge transfer occurs in an ultrafast manner within 100 fs, which notably increases the conductance of the device. Further analysis shows that the resonant charge transport is directly assisted by the B_(2) and A1 molecular vibration modes. Our study provides atomic insights into the time-dependent charge transport dynamics in single-molecule junctions, which is important for designing highly efficient single-molecule devices.

Contrasting Transport Performance of Electron-and Hole-Doped Epitaxial Graphene for Quantum Resistance Metrology

Epitaxial graphene grown on silicon carbide(Si C/graphene)is a promising solution for achieving a highprecision quantum Hall resistance standard.Previous research mainly focused on the quantum resistance metrology of n-type Si C/graphene,while a comprehensive understanding of the quantum resistance metrology behavior of graphene with different doping types is lacking.Here,we fabricated both n-and p-type Si C/graphene devices via polymer-assisted molecular adsorption and conducted systematic magneto-transport measurements in a wide parameter space of carrier density and temperature.It is demonstrated that n-type devices show greater potential for development of quantum resistance metrology compared with p-type devices,as evidenced by their higher carrier mobility,lower critical magnetic field for entering quantized Hall plateaus,and higher robustness of the quantum Hall effect against thermal degeneration.These discrepancies can be reasonably attributed to the weaker scattering from molecular dopants for n-type devices,which is further supported by the analyses on the quantum interference effect in multiple devices.These results enrich our understanding of the charged impurity on electronic transport performance of graphene and,more importantly,provide a useful reference for future development of graphene-based quantum resistance metrology.

Electron-Exciton Coupling in 1T-TiSe_(2)Bilayer

Excitons in solid state are bosons generated by electron-hole pairs as the Coulomb screening is sufficiently reduced.The exciton condensation can result in exotic physics such as super-fluidity and insulating state.In charge density wave(CDW)state,1T-TiSe_(2) is one of the candidates that may host the exciton condensation.However,to envision its excitonic effect is still challenging,particularly at the two-dimensional limit,which is applicable to future devices.Here,we realize the epitaxial 1T-TiSe_(2) bilayer,the two-dimensional limit for its 2×2×2 CDW order,to explore the exciton-associated effect.By means of high-resolution scanning tunneling spectroscopy and quasiparticle interference,we discover an unexpected state residing below the conduction band and right within the CDW gap region.As corroborated by our theoretical analysis,this mysterious phenomenon is in good agreement with the electron-exciton coupling.Our study provides a material platform to explore exciton-based electronics and opto-electronics.

凝聚态体系中激发态载流子动力学研究

激发态动力学是凝聚态物理中至关重要且富有挑战的科学问题,不仅需要从时间、空间、能量和动量等多个维度来描述,同时还需要考虑各种准粒子的相互作用以及多体效应.本文聚焦凝聚态体系激发态动力学的理论和应用研究,结合含时密度泛函、GW-BSE与面跳跃方法,发展了激发态动力学第一性原理计算软件Hefei-NAMD,构建了可以同时从时间、空间、动量、能量、自旋等多个维度研究凝聚态体系激发态动力学的理论和程序框架,并实现了自旋分辨的GW+real-time BSE(GW+rtBSE)激子动力学.利用这套方法,研究了凝聚态体系激发态动力学的许多问题,包括界面电荷转移动力学、电子空穴复合动力学以及二维TMD材料的谷激子动力学等.这些研究从第一性原理计算的角度,模拟激发态载流子在实空间、能量空间和动量空间的含时演化,为凝聚态体系的激发态动力学及准粒子耦合过程提供了深刻细致的理解.

量子等离激元光子学在若干方向的最新进展

等离激元光子学是围绕表面等离激元的原理和应用的学科,是纳米光学的重要组成部分.表面等离激元的本质是局域在材料界面纳米尺度内的多电子元激发.这一元激发可以与电磁场强烈耦合,使得我们可以通过纳米尺度结构接收,调控和辐射微米尺度光信息,并由此衍生出等离激元光子学的诸多应用.近年来,随着纳米加工尺度逼近量子极限,等离激元的量子特性受到了广泛关注.量子尺度的等离激元承接电子的波动性和光的粒子性,以其独特的內禀属性,在量子信息、高效光电器件、高灵敏探测等方面表现出十分诱人的前景.本综述重点介绍量子等离激元近年来的发展现状,回顾相关理论的发展以及与等离激元量子特性相关的一些突破性成果.最后对量子等离激元未来的发展进行了展望.

Atomically thin α-In2Se3: an emergent two-dimensional room temperature ferroelectric semiconductor

Room temperature ferroelectric thin films are the key element of high-density nonvolatile memories in modern electronics. However, with the further miniaturization of the electronic devices beyond the Moore’s law, conventional ferroelectrics suffer great challenge arising from the critical thickness effect, where the ferroelectricity is unstable if the film thickness is reduced to nanometer or single atomic layer limit. Two-dimensional(2D) materials, thanks to their stable layered structure, saturate interfacial chemistry, weak interlayer couplings, and the benefit of preparing stable ultra-thin film at 2D limit, are promising for exploring 2D ferroelectricity and related device applications. Therefore, it provides an effective approach to overcome the limitation in conventional ferroelectrics with the study of 2D ferroelectricity in van der Waals(vdW) materials. In this review article,we briefly introduce recent progresses on 2D ferroelectricity in layered vdW materials. We will highlight the study on atomically thin α-In2Se3, which is an emergent ferroelectric semiconductor with the coupled in-plane and out-of-plane ferroelectricity. Furthermore, two prototype ferroelectric devices based on ferroelectric α-In2Se3 will also be reviewed.

Two-dimensional Sb cluster superlattice on Si substrate fabricated by a two-step method

Nanoclusters consisting of a few atoms have attracted a lot of research interests due to their exotic size-dependent properties. Here, well-ordered two-dimensional Sb cluster superlattice was fabricated on Si substrate by a two-step method and characterized by scanning tunneling microscopy. High resolution scanning tunneling microscope measurements revealed the fine structures of the Sb clusters, which consist of several Sb atoms ranging from 2 to 7. Furthermore, the electronic structure of the nanocluster displays the quantized energy-level which is due to the single-electron tunneling effects. We believe that the fabrication of Sb cluster superlattice broadens the species of the cluster superlattice and provides a promising candidate to further explore the novel physical and chemical properties of the semimetal nanocluster.

In-Plane Magnetization-Induced Corner States in Bismuthene

We theoretically demonstrate that the electronic second-order topological insulator with robust corner states,having a buckled honeycomb lattice, can be realized in bismuthene by inducing in-plane magnetization. Based on the sp^(3) Slater–Koster tight-binding model with parameters extracted from first-principles results, we show that spin-helical edge states along zigzag boundaries are gapped out by the in-plane magnetization whereas four robust in-gap electronic corner states at the intersection between two zigzag boundaries arise. By regulating the orientation of in-plane magnetization, we show different position distribution of four corner states with different energies. Nevertheless, it respects some spatial symmetries and thus can protect the higher-order topological phase. Combined with the Kane–Mele model, we discuss the influence of the magnetization orientation on the position distribution of corner states.

Giant-Capacitance-Induced Wide Quantum Hall Plateaus in Graphene on LaAlO3/SrTiO3 Heterostructures

Hybrid structures of two distinct materials provide an excellent opportunity to optimize functionalities.We report the realization of wide quantum Hall plateaus in graphene field-effect devices on the LaAlO3/SrTiO3 heterostructures.Well-defined quantized Hall resistance plateaus at filling factors ν=±2 can be obtained over wide ranges of the magnetic field and gate voltage,e.g.,extending from 2 T to a maximum available magnetic field of 9 T.By using a simple band diagram model,it is revealed that these wide plateaus arise from the ultralarge capacitance of the ultra-thin LAO layer acting as the dielectric layer.This is distinctly different from the case of epitaxial graphene on Si C substrates,where the realization of giant Hall plateaus relies on the charge transfer between the graphene layer and interface states in SiC.Our results offer an alternative route towards optimizing the quantum Hall performance of graphene,which may find its applications in the further development of quantum resistance metrology.

Metal substrates-induced phase transformation of monolayer transition metal dichalcogenides for hydrogen evolution catalysis

Monolayer transition metal dichalcogenides can normally exist in several structural polymorphs with distinct electrical,optical,and catalytic properties.Effective control of the relative stability and transformation of different phases in these materials is thus of critical importance for applications.Using density functional theory calculations,we investigate the effects of low-work-function metal substrates including Ti,Zr,and Hf on the structural,electronic,and catalytic properties of monolayer MoS_(2) and WS_(2).The results indicate that such substrates not only convert the energetically stable structure from the 1H phase to the 1T'/1T phase,but also significantly reduce the kinetic barriers of the phase transformation.Furthermore,our calculations also indicate that the 1T' phase of MoS_(2) with Zr or Hf substrate is a potential catalyst for the hydrogen evolution reaction.

Prediction of quantum anomalous Hall effect in CrI_(3)/ScCl_(2)bilayer heterostructure

Based on first-principles calculations,a two-dimensional(2D)van der Waals(vd W)bilayer heterostructure consisting of two topologically trivial ferromagnetic(FM)monolayers CrI_(3)and ScCl_(2)is proposed to realize the quantum anomalous Hall effect(QAHE)with a sizable topologically nontrivial band gap of 4.5 me V.Its topological nature is attributed to an interlayer band inversion between the monolayers and critically depends on the symmetry of the stacking configuration.We further demonstrate that the topologically nontrivial band gap can be increased nearly linearly by the application of a perpendicular external pressure and reaches 8.1 me V at 2.7 GPa,and the application of an external out-of-plane electric field can also modulate the band gap and convert the system back to topologically trivial via eliminating the band inversion.An effective model is developed to describe the topological phase evolution in this bilayer heterostructure.This work provides a new candidate system based on 2D vd W materials for realization of potential high-temperature QAHE with considerable controllability.

Machine learning potential aided structure search for low-lying candidates of Au clusters

A machine learning(ML)potential for Au clusters is developed through training on a dataset including several different sized clusters.This ML potential accurately covers the whole configuration space of Au clusters in a broad size range,thus expressing a good performance in search of their global minimum energy structures.Based on our potential,the low-lying structures of 17 different sized Au clusters are identified,which shows that small sized Au clusters tend to form planar structures while large ones are more likely to be stereo,revealing the critical size for the two-dimensional(2D)to three-dimensional(3D)structural transition.Our calculations demonstrate that ML is indeed powerful in describing the interaction of Au atoms and provides a new paradigm on accelerating the search of structures.

Giant Rashba-like spin-orbit splitting with distinct spin texture in two-dimensional heterostructures

Based on first-principles density functional theory calculation,we discover a novel form of spin-orbit(SO)splitting in two-dimensional(2D)heterostructures composed of a single Bi(111)bilayer stacking with a 2D semiconducting In_(2)Se_(2) or a 2D ferroelectricα-In_(2)Se_(3) layer.Such SO splitting has a Rashba-like but distinct spin texture in the valence band around the maximum,where the chirality of the spin texture reverses within the upper spin-split branch,in contrast to the conventional Rashba systems where the upper branch and lower branch have opposite chirality solely in the region below the band crossing point.The ferroelectric nature ofα-In_(2)Se_(3) further enables the tuning of the spin texture upon the reversal of the electric polarization with the application of an external electric field.Detailed analysis based on a tight-binding model reveals that such SO splitting texture results from the interplay of complex orbital characters and substrate interaction.This finding enriches the diversity of SO splitting systems and is also expected to promise for spintronic applications.