石墨烯形核初期Cu(111)面上C_xH_y团簇生成的理论研究

采用基于密度泛函理论的第一原理计算方法,我们研究了Cu(111)表面上石墨烯成核生长过程中CxHy小团簇的吸附和生成行为.计算结果表明:随着氢原子饱和度、氢原子个数的增大,CxHy团簇的形成能减小,碳原子与铜表面的平均距离增加,C-C键的平均键长呈增大趋势.然而,当生成的CxHy团簇具有空间对称结构时,在一定程度上打破了上述规律性.令人惊奇的是,形成的C3H4和C3H5对称团簇具有类似石墨烯的空间结构,这类结构可能在石墨烯的形成过程中起着重要的作用.     

硅纳米团簇与石墨烯复合结构储锂性能的第一性原理研究

本文采用第一性原理计算方法, 研究了不同晶向硅纳米团簇与石墨烯复合结构稳定性及其储锂性能. 计算了不同高度、大小硅团簇与石墨烯复合结构的结合能, 复合结构中嵌锂吸附能和PDOS. 分析表明, 硅团簇和石墨烯之间形成较强的Si—C键, 其中[111]晶向硅团簇与石墨烯作用的形成能最高, 结构最为稳定. 进一步计算其嵌锂吸附能, 发现硅团簇中靠近石墨烯界面处的储锂位置更加有利于锂的吸附, 由于锂和碳、硅之间有较强电荷转移, 其吸附能明显大于其他储锂位置. 同时在锂嵌入过程中, 由于石墨烯的引入, 明显减小了界面处硅的形变, 有望提高其作为锂电池负极材料的可逆容量.     

第一性原理对Co_mAg_n(m+n=13)团簇的几何结构和性质的研究

本文利用第一性原理的广义梯度近似(GGA)对Co_mAg_n(m+n=13)团簇进行了研究,在几何优化计算的基础上,分析了Co_mAg_n(m+n=13)团簇的束缚能、能隙和磁性.结果表明:Co_mAg_n(m+n=13)团簇束缚能的二阶能量差分在m=6,8,10,12时出现峰值,说明Co6Ag7,Co8Ag5,Co10Ag3,Co12Ag1团簇相对稳定;能隙的研究说明Co6Ag7团簇较其他团簇有较高的化学稳定性;在Co_mAg_n(m+n=13)团簇中增加Co原子数目有助于磁性的增强.     

掺杂B_nN_n(n=12,16,20,24,28)团簇的生成热

中等尺寸的硼氮富勒烯笼与碳笼富勒烯相似,具有纳米尺度的球形内包空间,应该可以形成内包原子的笼状包合物,且无论从理论研究,还是从应用研究上讲都还处于起步阶段.我们采用第一性原理方法计算了第一、二、三、四周期内各元素原子作为M原子,分别构建M@B_nN_n(n=12,16,20)包合物并计算结合能.发现当硼氮富勒烯笼直径较小时,不同元素结合能的大小规律与原子半径的规律相符.副族元素的Mn、Fe、Co和Ni较其它元素的包合物稳定性明显增加.     

第一性原理对Al_mSi_n(m=1,2;n=1～6)团簇结构与性质的研究

本文运用第一性原理对Al_mSi_n（m=1,2;n=1～6）团簇的结构与性质进行了研究.在BLYP的水平上进行了结构优化和频率分析,得到了团簇的最低能量结构.同时计算和讨论了A1_msi_n团簇的束缚能、总能的二阶能量差分和分裂能以及费米能随原子数的变化.研究结果表明:Al_mSi_n团簇在m+n<4时的几何结构是平面结构,从4个原子开始转为空间的立体结构;除AlSi₃和Al₂Si₂团簇外,Al_mSi_n（m=1,2;n=1～6）团簇的束缚能随原子数增加而减小;分析A1_mSi_n（m=1,2;n=1～6）团簇的二阶能量差分和分裂能发现:在m+n=3,5时,团簇都出现较稳定的结构.     

第一性原理对(NaP3)n(n=1～5)团簇的几何结构和性质的研究

本文采用第一性原理研究了(NaP3)n(n=1～5)团簇的几何结构、能隙、电荷分布以及态密度.研究结果表明: NaP3团簇为线型结构,是(NaP3)n(n=1～5)团簇中的基本单元,随着n增大,团簇转变为环状结构和空间结构,; (NaP3)3团簇的能隙出现峰值, 表明该团簇较其他团簇有较高的稳定性; (NaP3)3团簇中对于高能量区域的态密度是由Na 3s和P 3p轨道贡献,其中在费米附近的能量主要由P 3p轨道贡献, 对于低能量区域的态密度主要由Na 3s轨道贡献; (NaP3)n(n=1～5)团簇中的Na原子电荷分布均为正值, 表明电荷总体上是从Na原子转移到P原子.     

第一性原理对(NaP_3)_n(n=1～5)团簇的几何结构和性质的研究

本文采用第一性原理研究了(NaP_3)_n(n=1~5)团簇的几何结构、能隙、电荷分布以及态密度.研究结果表明:NaP_3团簇为线型结构,是(NaP_3)_n(n=1~5)团簇中的基本单元,随着n增大,团簇转变为环状结构和空间结构;(NaP_3)_3团簇的能隙出现峰值,表明该团簇较其他团簇有较高的稳定性;(NaP_3)_3团簇中对于高能量区域的态密度是由Na 3s和P 3p轨道贡献,其中在费米附近的能量主要由P 3p轨道贡献,对于低能量区域的态密度主要由Na 3s轨道贡献;(NaP_3)_n(n=1~5)团簇中的Na原子电荷分布均为正值,表明电荷总体上是从Na原子转移到P原子.     

第一性原理对(NaP3)n(n=1～5)团簇的几何结构和性质的研究

本文采用第一性原理研究了(NaP3)n(n=1～5)团簇的几何结构、能隙、电荷分布以及态密度.研究结果表明: NaP3团簇为线型结构,是(NaP3)n(n=1～5)团簇中的基本单元,随着n增大,团簇转变为环状结构和空间结构,; (NaP3)3团簇的能隙出现峰值, 表明该团簇较其他团簇有较高的稳定性; (NaP3)3团簇中对于高能量区域的态密度是由Na 3s和P 3p轨道贡献,其中在费米附近的能量主要由P 3p轨道贡献, 对于低能量区域的态密度主要由Na 3s轨道贡献; (NaP3)n(n=1～5)团簇中的Na原子电荷分布均为正值, 表明电荷总体上是从Na原子转移到P原子.     

第一性原理对ComAgn（m+n=13）团簇的几何结构和性质的研究

本文利用第一性原理的广义梯度近似（GGA)对ComAgn（m+n=13）团簇进行了研究.在几何优化计算的基础上,分析了ComAgn（m+n=13）团簇的束缚能、能隙和磁性;结果表明： ComAgn（m+n=13）团簇束缚能的二阶能量差分在m =6,8,10,12时出现峰值,说明Co6Ag7, Co8Ag5, Co10Ag3, Co12Ag1团簇相对稳定;同时,能隙的研究说明Co6Ag7团簇较其他团簇有较高的化学稳定性;在ComAgn（m+n=13）团簇中增加Co原子数目有助于磁性的增强.     

(CuSe)_n(n=1-10)团簇结构稳定性与磁性的理论研究

本文采用包含广义梯度近似的密度泛函理论对铜、硒二元团簇(CuSe)_n(n=1-10)的结构稳定性与磁性质进行系统的研究,发现:(CuSe)_n(n=1-10)二元团簇的原子总数为8时几何结构出现由平面向立体的转变行为,且Cu3Se3为"幻数"构型.同时,(CuSe)_n(n=1-10)团簇的平均结合能比同尺寸单质铜团簇的大,因此混合团簇(CuSe)_n(n=1-10)具有比单质铜团簇更强的稳定性;另外,根据(CuSe)_n(n=1-10)团簇的二阶差分能和HOMO-LUMO能隙随尺寸增加的演化趋势可获知,Cu8Se8的结构极其稳定.最后,对团簇磁性的研究发现,铜硒团簇展现出比较特别的磁性,其中,Cu3Se3的总磁矩为3μB,且磁性主要来源于硒原子,而当n=4,6,8和10时,(CuSe)_n(n=1-10)团簇磁性出现淬灭现象.     

Theoretical study of the initial stage of InN growth on cubic zirconia (111) substrates

An initial stage of InN growth on cubic zirconia (111) substrates has been investigated using first‐principles calculations based on density functional theory (DFT). We have evaluated adsorption energies of indium and nitrogen atoms on cubic zirconia (111) surfaces, and have found that the differences in the adsorption energies of the indium atoms at various adsorption sites were small, indicating that the migration of the indium atoms on zirconia (111) surfaces occurs readily. On the other hand, we have found that the differences in the adsorption energies of the nitrogen atoms at various adsorption sites were large, implying that the nitrogen atoms tend to stay at the stable site with the largest adsorption energy, which was identified as the O–Zr bridge site. These results suggest that the first layer of InN films is the nitrogen layer. In addition, we have found that the energetically favorable arrangement is comprised of InN(0001)//cubic zirconia (111) and InN $ [11\bar 20] $ //cubic zirconia $ [1 \bar 10], $ which is quite consistent with previously obtained experimental data. Furthermore, the hybridization effect between N 2p and O 2p plays a crucial role in determining the interface structure for the growth of InN on cubic zirconia (111) surfaces. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Vibrational properties of small cobalt clusters on the Cu(111) surface

Physics of the Solid State - Vibrational properties of small cobalt clusters (dimer and trimer) adsorbed on the Cu(111) surface are studied using interatomic interaction potentials obtained in a...     

Theoretical study of the Cl-passivated Si(111) surface

The Cl-passivated Si(111) surface is studied using density functional theory, in conjunction with the B3LYP functional and the cluster model. We compute the Si–Cl frequency and the Si–Cl bond energy for R₃SiCl, and the abstraction barrier for the reaction R₃SiCl+H→R₃Si+HCl using the B3LYP approach. We calibrate the B3LYP bond energy and the abstraction barriers using the values obtained using the G2MP2, G2 and CCSD(T) approaches. Our computed B3LYP Si–Cl frequency of 555 cm⁻¹ is in good agreement with the experimental value of 588 cm⁻¹. The shift in the Si–Cl frequency as surface chlorine is added to the cluster agrees with experimental observations.     

Superparamagnetism in small Fe clusters on Cu(111)

Fe clusters of 105±2 atoms/cluster were mass selectively deposited onto Cu(111) at cryogenic temperatures. XMCD was used to measure temperature and direction dependent magnetization curves. The clusters are superparamagnetic at the lowest temperature measured (10 K). Their magnetization curves are consistent with magnetic moments of ≈2.5μ_B per atom which are thus enhanced over the bulk values. Within experimental accuracy, the clusters do not present magnetocrystalline anisotropy in the temperature range of 10 K to 60 K.     

Formation and diffusion of S-decorated Cu clusters on Cu(111)

S-decorated Cu trimers are a likely agent of S-enhanced Cu transport between islands on Cu(111). According to ab initio calculations, excellent S bonding to trimer-Cu dangling valence results in an ad- Cu(3)S(3) formation energy of only approximately 0.28 eV, compared to 0.79 eV for a self-adsorbed Cu atom, and a diffusion barrier < or =0. 35 eV.     

Static investigation of the small clusters on the Cu(111) and Au(111) surfaces

The diffusion properties of small clusters Ag_n, Cu_n, and Au_n on the Cu(111) and Au(111) surfaces were studied using the molecular statics (MS) in order to understand the atomistic processes underlying the motion. In this work, the atomic interaction potential is modeled by a semi-empirical Embedded Atom Method (EAM), while the drag method is used to determine the static activation energy for each diffusion path. The presented results indicate that the dimer can diffuse on the (111) surface via the zig-zag and concerted motion mechanisms. The trimer diffuses according to the concerted motion mechanism. For the tetramer diffusion, the mechanism that consumes the least amount of energy is the zig-zag motion, in which only two atoms are needed for the diffusion process at one time. This allows finding a static activation energy smaller compared to the trimer diffusion.     

Atom deposition on surface clusters: thin film growth on Pd(111)

We have studied the vapor phase deposition of single metal atoms on two-dimensional clusters at the Pd(111) surface. The system considered here are heptamers and dodecamers for the substrate temperature of 100 K. Using molecular dynamics simulations with the corrected effective medium potentials for Pd, Cu and Rh, we have found that an adatom either diffuses on the cluster or incorporates itself into the cluster depending on the size of clusters and the kind of metals in the gas/cluster system. We also discovered that incorporation of a deposited gas atom into a surface cluster at 100 K was not a consequence of the reduction of the barrier heights at the step edges and that the type of post-impact dynamics for hexagonal heptamers depends on the impact point.     

Adsorption behavior of iron phthalocyanine at the initial stage on Cu(100) surface

The adsorption behavior of iron phthalocyanine (FePc) on the Cu(100) surface at the initial stage has been investigated by combining scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. At low coverage, FePc molecules deposited on the sample surface at room temperature tend to adsorb dispersedly with their molecular planes parallel to the crystallographic directions of the substrate. Another interesting STM observation for the sub-monolayer coverage is that the molecular axes of FePc are aligned along [037] (as well as $\left[0\overline{3}7\right]$) azimuth. At the monolayer coverage and elevated temperature, two types of ordered structures are observed. The FePc adsorption sites for the experimentally observed two distinct ordered domains have been revealed through DFT calculations. With further increasing the coverage, molecular clusters are formed particularly near the step edges.