采用(meta)-GGA泛函对Ag(111)、Rh(111)和Ir(111)上乙烯吸附的理论研究

本文针对在多种催化反应的重要中间体乙烯,使用(meta)-GGA等级的包含PBE,BEEF-vdW,SCAN以及SCAN+rVV10在内的多种交换关联泛函,系统研究了在过渡金属表面(Ag,Rh和Ir)上乙烯吸附势能面对泛函的依赖关系. 研究发现,对于乙烯在贵金属Ag(111)上的吸附,除了PBE外,BEEF-vdW,SCAN以及SCAN+rVV10均能预测出物理吸附态的存在. 对于乙烯在Rh(111)面的吸附,SCAN和SCAN+rVV10预测在化学吸附位之前存在有物理吸附前驱态,而基于PBE和BEEF-vdW的势能面并没有发现前驱态的存在. 而对于乙烯在Ir(111)上的吸附,BEEF-vdW也能微弱地预测出化学吸附前驱态的存在. 研究结果表明,无论在哪一种金属表面上,四种泛函中SCAN+rVV10给出的吸附能最强,其次是SCAN,最后是PBE或者BEEF-vdW.     

交换关联泛函近似方法对Ru催化剂上甲烷和乙烷形成的影响

密度泛函理论作为多相催化研究中的一个强有力工具,常被用于获得催化过程中关键的热力学及动力学参数,如吸附能、反应焓、活化能垒和速率常数等. 理解密度泛函交换关联近似方法对于揭示催化剂的催化性能及机理至关重要. 本文报道了六种不同的交换关联泛函近似方法,包括PBE、RPBE、BEEF+vdW、optB86b+vdW、SCAN和SCAN+rVV10,对金属Ru(0001)和Ru(1011)表面上甲烷和乙烷形成过程中涉及到的中间体的吸附能、反应能和活化能垒的影响. 当基元反应中反应物和产物与表面的配位数不同时,理论计算的反应能大小强烈依赖于交换关联密度泛函的选择. 对于涉及多个基元步骤的总反应,反应能的计算偏差会逐渐累积,从而导致不同的交换关联泛函近似方法之间的巨大差异. 由于不同泛函对反应涉及到的中间体吸附能之间存在差异,交换关联泛函近似方法的选择显著地影响Ru(0001)表面上甲烷、乙烯和乙烷的选择性. 然而,不同泛函近似方法对于Ru(0001) 和Ru(1011)表面上基元反应的能垒以及结构敏感性影响不大. 本工作不仅揭示了交换关联密度泛函近似方法在理论计算研究催化领域的局限性,也强调了选择合适的交换关联泛函方法对于正确评估催化剂活性和选择性的重要性.     

To wet or not to wet? Dispersion forces tip the balance for water ice on metals

Despite widespread discussion, the role of van der Waals dispersion forces in wetting remains unclear. Here we show that nonlocal correlations contribute substantially to the water-metal bond and that this is an important factor in governing the relative stabilities of wetting layers and 3D bulk ice. Because of the greater polarizability of the substrate metal atoms, nonlocal correlations between water and the metal exceed those between water molecules within ice. This sheds light on a long-standing problem, wherein common density functional theory exchange-correlation functionals incorrectly predict that none of the low temperature experimentally characterized icelike wetting layers are thermodynamically stable.     

二维范德瓦尔斯异质结构的制备与物性研究

二维范德瓦尔斯材料(可简称二维材料)已发展成为备受瞩目的材料大家族,而由其衍生的二维范德瓦尔斯异质结构的集成、性能及应用是现今凝聚态物理和材料科学领域的研究热点之一.二维范德瓦尔斯异质结构为探索丰富多彩的物理效应和新奇的物理现象,以及构建新型的自旋电子学器件提供了灵活而广阔的平台.本文从二维材料的转移技术着手,介绍二维范德瓦尔斯异质结构的构筑、性能及应用.首先,依据湿法转移和干法转移的分类,详细介绍二维范德瓦尔斯异质结构的制备技术,内容包括转移技术的通用设备、常用转移方法的具体操作步骤、三维操纵二维材料的方法、异质界面清洁.随后介绍二维范德瓦尔斯异质结构的性能和应用,重点介绍二维磁性范德瓦尔斯异质结构,并列举在二维范德瓦尔斯磁隧道结和摩尔超晶格领域的应用.因此,二维材料转移技术的发展和优化将进一步助力二维范德瓦尔斯异质结构在基础科学研究和实际应用上取得突破性的成果.     

A coupled cluster treatment of intramonomer electron correlation within symmetry-adapted perturbation theory: benchmark calculations and a comparison with a density-functional theory description

Symmetry-adapted perturbation theory (SAPT) with intramonomer electron correlation described by coupled cluster theory limited to single and double excitations was applied to 21 noncovalent complexes in their minimum geometries. The resulting benchmark contributions to the interaction energy were utilized to examine the accuracy of a more approximate variant of the SAPT method, where interacting molecules are described by density functional theory (DFT) with different functionals, like LDA, PBE, B3LYP, PBE0, M05, M05-2X, M06, and M06-2X (in all cases the asymptotic correction for the exchange-correlation functional has been utilized). Average errors for individual energy components of SAPT(DFT) are not larger than 10% for best functionals under study. Among the tested functionals PBE0, M05, and B3LYP should be especially recommended for the SAPT(DFT) approach. The M06 functional gives the largest errors with respect to SAPT(CCSD) and should not be used for describing intramonomer correlation in SAPT.     

二维范德瓦尔斯异质结构的制备与物性研究

二维范德瓦尔斯材料(可简称二维材料)已发展成为备受瞩目的材料大家族,而由其衍生的二维范德瓦尔斯异质结构的集成、性能及应用是现今凝聚态物理和材料科学领域的研究热点之一.二维范德瓦尔斯异质结构为探索丰富多彩的物理效应和新奇的物理现象,以及构建新型的自旋电子学器件提供了灵活而广阔的平台.本文从二维材料的转移技术着手,介绍二维范德瓦尔斯异质结构的构筑、性能及应用.首先,依据湿法转移和干法转移的分类,详细介绍二维范德瓦尔斯异质结构的制备技术,内容包括转移技术的通用设备、常用转移方法的具体操作步骤、三维操纵二维材料的方法、异质界面清洁.随后介绍二维范德瓦尔斯异质结构的性能和应用,重点介绍二维磁性范德瓦尔斯异质结构,并列举在二维范德瓦尔斯磁隧道结和摩尔超晶格领域的应用.因此,二维材料转移技术的发展和优化将进一步助力二维范德瓦尔斯异质结构在基础科学研究和实际应用上取得突破性的成果.     

描述甲烷在Pt(110)-(21)表面的化学吸附解离的密度泛函评估

本文探讨了几种梯度近似(GGA)密度泛函及元梯度近似(meta-GGA)密度泛函在描述甲烷在重构的Pt(110)-(2×1)上的解离化学吸附作用的适用性. 金属的体相和表面结构、甲烷的吸附能量和解离能垒等被用来评估泛函的可靠性. 另外,在从头算分子动力学计算中,采用范德瓦尔斯矫正的GGA函数(optPBE-vdW)和范德瓦尔斯矫正的meta-GGA函数(MS-PBEl-rVV10）计算粘附概率. 计算结果表明,使用这两种泛函能更好地与现有的实验结果吻合,从而为发展甲烷在Pt(110)-(2×1)表面解离的可靠机器学习势能面打下重要基础.     

Hydrogen bonds and van der waals forces in ice at ambient and high pressures

The first principles methods, density-functional theory and quantum Monte Carlo, have been used to examine the balance between van der Waals (vdW) forces and hydrogen bonding in ambient and high-pressure phases of ice. At higher pressure, the contribution to the lattice energy from vdW increases and that from hydrogen bonding decreases, leading vdW to have a substantial effect on the transition pressures between the crystalline ice phases. An important consequence, likely to be of relevance to molecular crystals in general, is that transition pressures obtained from density-functional theory exchange-correlation functionals which neglect vdW forces are greatly overestimated.     

Asymptotics of the dispersion interaction: analytic benchmarks for van der Waals energy functionals

We show that the usual sum of R-6 contributions from elements separated by distance R can give qualitatively wrong results for the electromagnetically nonretarded van der Waals interaction between nonoverlapping bodies. This occurs for anisotropic nanostructures that have a zero electronic energy gap, such as metallic nanotubes or nanowires, and nanolayered systems including metals and graphene planes. In all these cases our analytic microscopic calculations give an interaction falling off with a power of separation different from the conventional value. We discuss implications for van der Waals energy functionals. The new nanotube interaction might be directly observable at submicron separations.     

van der Waals interactions between thin metallic wires and layers

Quantum Monte Carlo (QMC) methods have been used to obtain accurate binding-energy data for pairs of parallel thin metallic wires and layers modeled by 1D and 2D homogeneous electron gases. We compare our QMC binding energies with results obtained within the random phase approximation, finding significant quantitative differences and disagreement over the asymptotic behavior for bilayers at low densities. We have calculated pair-correlation functions for metallic biwire and bilayer systems. Our QMC data could be used to investigate van der Waals energy functionals.     

范德瓦尔斯磁性材料CrOCl变磁性相变的磁力显微镜研究

近年来,二维范德瓦尔斯磁性材料因为在自旋电子学的应用前景而吸引了广泛的关注.CrOCl是一种范德瓦尔斯磁性材料,理论预言其单层具有高达160 K的居里温度,因此吸引了广泛的关注。为了更好的理解这一材料的磁性,我们利用磁力显微镜研究了CrOCl变磁性相变中磁畴结构随磁场的变化。实验发现,在2K下CrOCl样品表面出现随磁场变化的方格条纹,给出了变磁性相比中反铁磁相和铁磁相竞争的图样,并通过二维快速傅里叶变换证实了CrOCl磁性的各向异性。我们的结果为后续研究CrOCl薄层的磁性提供了参考依据。     

Adsorption of Cu, Ag, and Au atoms on graphene including van der Waals interactions

We performed a systematic density functional (DF) study of the adsorption of copper, silver, and gold adatoms on pristine graphene, especially accounting for van der Waals (vdW) interactions by the vdW-DF and PBE + D2 methods. In particular, we analyze the preferred adsorption site (among top, bridge, and hollow positions) together with the corresponding distortion of the graphene sheet and identify diffusion paths. Both vdW schemes show that the coinage metal atoms do bind to the graphene sheet and that in some cases the buckling of the graphene layer can be significant. Only the results for silver are qualitatively at variance with those obtained with the generalized gradient approximation, which gives no binding in this case. However in all three cases, we observe some quantitative differences between the vdW-DF and PBE + D2 methods. For instance the adsorption energies calculated with the PBE + D2 method are systematically higher than the ones obtained with vdW-DF. Moreover, the equilibrium distances computed with PBE + D2 are shorter than those calculated with the vdW-DF method.     

Tuning band alignment and optical properties of 2D van der Waals heterostructure via ferroelectric polarization switching

Favourable band alignment and excellent visible light response are vital for photochemical water splitting. In this work, we have theoretically investigated how ferroelectric polarization and its reversibility in direction can be utilized to modulate the band alignment and optical absorption properties. For this objective, 2D van der Waals heterostructures (HTSs) are constructed by interfacing monolayer MoS₂ with ferroelectric In2Se3. We find the switch of polarization direction has dramatically changed the band alignment, thus facilitating different type of reactions. In In₂Se₃/MoS₂/In₂Se₃ heterostructures, one polarization direction supports hydrogen evolution reaction and another polarization direction can favour oxygen evolution reaction. These can be used to create tuneable photocatalyst materials where water reduction reactions can be selectively controlled by polarization switching. The modulation of band alignment is attributed to the shift of reaction potential caused by spontaneous polarization. Additionally, the formed type-II van der Waals HTSs also significantly improve charge separation and enhance the optical absorption in the visible and infrared regions. Our results pave a way in the design of van der Waals HTSs for water splitting using ferroelectric materials.     

Improved semiconductor lattice parameters and band gaps from a middle-range screened hybrid exchange functional

We show that the middle-range exchange-correlation hybrid of Henderson, Izmaylov, Scuseria and Savin (HISS) performs extremely well for elemental and binary semiconductors with narrow or visible spectrum band gaps, as well as some wider gap or more ionic systems used in devices. The lattice parameters are superior to those predicted by the screened hybrid functional of Heyd, Scuseria and Ernzerhof (HSE), and provide a significant improvement over the geometries predicted by typical semilocal functionals, yielding results competitive with PBEsol, which was specially tuned for solids. HISS also yields band gaps superior to those produced by functionals developed specifically for the solid state. Timings indicate that HISS is more computationally efficient than HSE, implying that the high quality lattice constants coupled with improved optical band gap predictions render HISS a useful adjunct to HSE in the modeling of geometry-sensitive semiconductors.     

Methane adsorption on graphene from first principles including dispersion interaction

The methane–graphene interaction is studied using density functional theory complemented with a semiempirical dispersion correction scheme (DFT-D), an ab initio van der Waals density functional (vdW-DF) ansatz as well as using Møller Plesset perturbation theory (MP2). The adsorption energy of 0.17 eV and the molecular distance of 3.28 Å obtained from the MP2 calculations are close to the experimental data, while the vdW-DF scheme results either in a realistic adsorption energy or a realistic adsorption geometry, depending on the underlying exchange-correlation functional. The present implementation of DFT-D overbinds about as much as bare DFT calculations underbind, but yields a meaningful adsorption height.     

A self-driven photodetector based on a SnS2/WS2 van der Waals heterojunction with an Al2O3 capping layer

Photodetectors based on two-dimensional (2D) materials have attracted considerable attention because of their unique properties. To further improve the performance of self-driven photodetectors based on van der Waals heterojunctions, a conductive band minimum (CBM) matched self-driven SnS₂/WS₂ van der Waals heterojunction photodetector based on a SiO₂/Si substrate has been designed. The device exhibits a positive current at zero voltage under 365 nm laser illumination. This is attributed to the built-in electric field at the interface of the SnS₂ and WS₂ layer, which will separate and transport the photogenerated carriers, even at zero bias voltage. In addition, the Al₂O₃ layer is covered by the surface of the SnS₂/WS₂ photodetector to further improve the performance, because the Al₂O₃ layer will introduce tensile stress on the surface of the 2D materials leading to a higher electron concentration and smaller effective mass of electrons in the films. This work provides an idea for the research of self-driven photodetectors based on a van der Waals heterogeneous junction.     

Metal-to-insulator transition in two-dimensional ferromagnetic monolayer induced by substrate

Two-dimensional(2D) ferromagnetic(FM) materials have great potential for applications in next-generation spintronic devices. Since most 2D FM materials come from van der Waals crystals, stabilizing them on a certain substrate without killing the ferromagnetism is still a challenge. Through systematic first-principles calculations, we proposed a new family of 2D FM materials which combines TaX(X = S, Se or Te) monolayer and Al_2O_3(0001) substrate. The TaX monolayers provide magnetic states and the Al_2O_3(0001) substrate stabilizes the former. Interestingly, the Al_2O_3(0001)substrate leads to a metal-to-insulator transition in the Ta X monolayers and induces a band gap up to 303 meV. Our study paves the way to explore promising 2D FM materials for practical applications in spintronics devices.