V_nB_(8(n+1))~-(n=1-3)团簇的几何结构、电子和光谱特性

基于密度泛函理论和卡里普索结构预测方法,系统研究了V_nB_(8(n+1))~-(n=1-3)团簇的几何结构、电子和光谱特性.首先,利用卡里普索结构预测方法确定了VB_(16)~-的基态结构为高对称性的C_(2v)点群对称结构.在此基态结构基础上,通过堆积的方式优化得到了V_2B_(24)~-和V_3B_(32)~-团簇的基态结构.结果显示,V_2B_(24)~-和V_3B~(32)~-团簇分别拥有高对称性的C_(4h)和D_(8d)点群对称结构.基于上述基态结构,系统分析了不同尺寸团簇的自然布局分布和自然电子组态、Mayer键级和电子局域函数.最后,讨论了不同团簇的红外、拉曼光谱等光谱特性,为过渡金属钒掺杂硼基纳米材料的研究提供理论参考.     

理论研究B3Sin0\- (n=15-20)团簇的几何结构、稳定性和电子特性

基于B3LYP/6-311+G(d)下的密度泛函理论和卡里普索结构预测方法,系统研究了B3Sin0\- (n=15-20)团簇的几何结构、稳定性和电子特性。结构搜索发现,三个硼原子易构成三角结构并包裹在硅团簇笼子中。并通过对比实验和理论的光电子谱,进一步确定基态结构的合理性。此外,利用平均结合能、二阶差分能、最高占据轨道和最低未占据轨道能隙研究了体系的稳定性。最后,讨论了体系电荷的分布和转移、红外和拉曼谱等电子特性。     

Probing structural and electronic properties of divalent metal Mgn+1 and SrMgn (n=2–12) clusters and their anions

Divalent metal clusters have received great attention due to the interesting size-induced nonmetal-to-metal transition and fascinating properties dependent on cluster size,shape,and doping.In this work,the combination of the CALYPSO code and density functional theory(DFT)optimization is employed to explore the structural properties of neutral and anionic Mg_n+1 and SrMgn(n=2-12)clusters.The results exhibit that as the atomic number of Mg increases,Sr atoms are more likely to replace Mg atoms located in the skeleton convex cap.By analyzing the binding energy,second-order energy difference and the charge transfer,it can be found the SrMg9 cluster with tower framework presents outstanding stability in a studied size range.Further,bonding characteristic analysis reveals that the stability of SrMg9 can be improved due to the strong s-p interaction among the atomic orbitals of Sr and Mg atoms.     

MB80/-1（M=Li、Na、Rb）团簇几何结构及电子特性研究

本文结合CALYPSO软件和密度泛函理论,详细研究了MB80/- (M=Li､Na､Rb､Cs)团簇的几何结构和成键特性｡结构分析结果表明,MB80/- (M=Li､Na､Rb､Cs)团簇的基态结构都具有相似的几何构型,均为七棱锥状结构,并且随着掺杂原子的原子序数的增加,其M-B键的键长呈增加的趋势｡通过稳定性分析,我们发现LiB8-团簇的HOMO-LOMO能隙以及结合能Eb最大,因此这个团簇是体系中相对稳定的结构｡电荷转移分析表明,掺杂的碱金属原子在所研究体系中充当着电子供体的角色｡最后,成键分析的结果显示,LiB8-团簇的稳定性来源于B原子的2p轨道以及Li原子的2s和2p轨道在HOMO和LUMO的高贡献;适应性自然密度划分分析显示, B和Li原子都参与了成键,这同样有利于LiB8-团簇的高稳定性的形成｡希望我们的工作能为进一步研究碱金属掺杂硼团簇提供指导和帮助｡     

Structure search of two-dimensional systems using CALYPSO methodology

The dimensionality of structures allows materials to be classified into zero-, one-, two-, and threedimensional systems. Two-dimensional (2D) systems have attracted a great deal of attention and typically include surfaces, interfaces, and layered materials. Due to their varied properties, 2D systems hold promise for applications such as electronics, optoelectronics, magnetronics, and valleytronics. The design of 2D systems is an area of intensive research because of the rapid development of ab initiostructure-searching methods. In this paper, we highlight recent research progress on accelerating the design of 2D systems using the CALYPSO methodology. Challenges and perspectives for future developments in 2D structure prediction methods are also presented.     

Structural,Thermal, and Electronic Properties of Two-Dimensional Gallium Oxide (β-Ga2O3) from First-Principles Design

Two-dimensional (2D) materials with exotic electronic, optical and mechanical properties have attracted tremendous attention in the last two decades, due to their potential applications in electronics, energy storage and conversion technologies. However, only a few dozen 2D materials have been successfully synthesized or exfoliated. Motivated by the recent discovery of 2D gallenene, we have explored new 2D allotropes of β-Ga₂O₃, an emerging wide-band gap transparent conductive oxide (TCO) with a wide range of semiconducting applications. All the possible 2D allotropes of β-Ga₂O₃ with high energetic stability have been predicted using particle swarm optimization, combined with density functional theory calculations. The structural and dynamical stability of the predicted 2D allotropes has been analyzed. Although β-Ga₂O₃ is not a van der Waals material, results predict that one or two allotropes of β-Ga₂O₃ are stable. In addition, the accurate band structures of these 2D semiconducting oxides have been calculated using both the GGA and LDA-1/2 approach. Remarkably, monolayer Ga₂O₃(100) has a larger indirect band gap of 4 eV, demonstrating a new avenue for the discovery of 2D β-Ga₂O₃ based nano-devices with enhanced electronic properties.     

VB2n-(n=8~12)团簇几何结构、电子及热力学特性的理论研究

基于卡里普索结构预测程序和密度泛函理论的第一性原理计算,搜索确定了VB_2n^-（n=8~12）团簇的基态和亚稳态结构。结果发现,V原子的掺杂完全改变了原硼团簇的结构并提高了原体系的稳定性。掺杂体系基态结构分别呈现高对称性的鼓状（VB₁₆^-：C_2v）、管状（VB₁₈^-：C_2v和VB₂₀^-：C_s）及笼状（VB₂₂^-：C₂和VB₂₄^-：D_3h）结构。基于基态结构,研究了体系的电荷转移和极化率,拟合出了光电子能谱、红外和拉曼谱图,分析了流变键和芳香特性。最后,研究了体系的热力学特性,讨论了温度对热力学参数的影响。     

Systematic theoretical investigation of structure and electronic properties of pure copper and lithium doped copper clusters

The pure copper and lithium-doped copper clusters are studied using the unbiased CALYPSO structure searching method and density function theory to understand the evolution of various structure and electronic properties. Theoretical results show the growth behaviours of doped clusters are organised as follows: Li capped Cu_n clusters or Li substituted Cu_n+1 clusters as well as Cu capped Cu_n-1Li clusters. Moreover, the lowest energy structures of Cu_nLi favour planar structures for n ≤ 3 and three-dimensional structures for n = 4–12. In addition, the calculated averaged binding energies, fragmentation energies and second-order difference of energies exhibit obvious odd–even alternations as cluster size increasing. At last, the highest occupied-lowest unoccupied molecular orbital gaps, molecular orbital energy, magnetic property, natural population analysis, natural electron configurations, electrostatic potential, electron density difference, Infrared and Raman spectra and density of states are also, respectively, operative for characterising and rationalising the electronic properties of doped clusters.