Structural and electronic properties of Snn-1Pb and Pbn-1Sn clusters: a theoretical investigation through first principles calculations

Here we report a systematic theoretical study of the structure and electronic properties of Sn_n-1Pb and Pb_n-1Sn (n = 2-13) clusters and compare these results with pure Sn_n and Pb_n to understand the influence of the dopant elements. The calculations were carried out using the density functional theory with generalized gradient approximation for the exchange-correlation potential. Extensive search based on large number of initial configurations has been carried out to locate the stable isomers of Sn_n-1Pb and Pb_n-1Sn (n = 2-13) clusters. The relative stability of Sn_n-1Pb and Pb_n-1Sn (n = 2-13) clusters is analyzed based on the calculated binding energies and second difference in energy. The stability analysis of these clusters suggests that, while the substitution of Sn by Pb lowers the stability of Sn_n clusters, presence of Sn enhances the stability of the Pb_n clusters. The results suggest that while for Sn_n-1Pb, n=4, 7, 10, 12 clusters are more stable than their respective neighbors, Pb_n-1Sn clusters with n = 4, 7 and 9 are found to be more stable. Based on the fragmentation pattern it is seen that for Sn_n-1Pb and Pb_n-1Sn clusters favor monomer evaporation of the Pb atom up to n =11 and n =12, respectively. Unlike this trend, the Sn₁₁Pb undergoes fission type fragment into Sn₅Pb and Sn₆ clusters. A comparison between our theoretical results and surface induced dissociation experiment shows good agreement, which gives confidence on the prediction of the ground state geometries.     

Relative stability of Sin and SinSc- clusters in the range n = 14–18

We present a first-principles pseudopotential optimization of the lower energy equilibrium structure of Si_nSc^- anions for n=14-18. We find that Si₁₆Sc^- is more stable than its neighbors clusters, in agreement with recent experimental mass spectra. We also optimize the geometry of pure Si_n neutral clusters in the range n=14-18, and compare our results with those from previous first-principles calculations.     

Metastable fragmentation of silver bromide clusters

The abundance spectra and the fragmentation channels of silver bromide clusters have been measured and analyzed. The most abundant species are Ag_nBr_{n - 1} ⁺ and Ag_nBr_{n + 1} ^- and Ag₁₄Br₁₃ ⁺ is a magic number, revealing their ionic nature. However, some features depart from what is generally observed for alkali-halide ionic clusters. From a certain size, Ag_nBr_{n - 1} ⁺ is no more the main series, and Ag_nBr _{n - 2, 3} ⁺ series become almost as important. The fast fragmentation induced by a UV laser makes the cations lose more bromine than silver ions and lead to more silver-rich clusters. Negative ions mass spectra contain also species with more silver atoms than required by stoichiometry. We have investigated the metastable fragmentation of the cations using a new experimental method. The large majority of the cations release mainly a neutral Ag₃Br₃ cluster. These decay channels are in full agreement with our recent ab initio DFT calculations, which show that Ag⁺-Ag⁺ repulsion is reduced due to a globally attractive interaction of their d orbitals. This effect leads to a particularly stable trimer (AgBr)₃ and to quasi-planar cyclic structures of (AgBr)_n clusters up to n = 6. We have shown that these two features may be extended to other silver halides, to silver hydroxides (AgOH)_n, and to cuprous halide compounds. Received 9 November 2000 and Received in final form 25 January 2001     

砷化镓离子团簇的稳定性研究

采用全势能线性糕模轨道分子动力学方法，详细研究了砷化镓离子团簇Ga_nAs_n(n=4，5，6)的几何结构和稳定性.分别找到了这些离子团簇的最低能量结构，通过计算发现这些结构明显不同于中性团簇的基态结构.还发现离子团簇的其他稳定结构与对应的中性结构相比也有较大的结构畸变.在这些砷化镓离子团簇中，相对于砷原子而言，镓原子更容易处在帽原子的位置上. 关键词： 离子团簇 基态结构 稳定性     

关于Al_nC和Al_nC~+(n=1—8)团簇结构和稳定性的研究

通过采用7种密度泛函理论DFT方法对AlnC进行计算,所得结果与实验数据比较,选择了B3lyp方法和6-311G(d)基组对AlnC及AlnC+(n=1—8)团簇进行结构优化和频率分析,得到了AlnC及AlnC+基态以及亚稳态结构.当n从小到大变化时,这些团簇的结构从平面向立体过渡,平面构型以三角形为主,立体构型主要是三棱柱笼状结构;在这些团簇中的高对称性结构中,中性团簇和阳离子只能有其一是稳定构型;在所研究的团簇中,Al2C和Al5C团簇较为稳定.     

Study of clusters of interest for liquid ionic alloys

Calculations are reported of the total energies and related quantities of sequences of small clusters of the form A_m Pb_n, where A is an alkali atom, n <6 and m < 9. The object of this study is to shed light on the stoichiometry and the possible formation of complexes in A-Pb liquid alloys. The calculations are performed using empty core pseudopotentials and the spherical average approximation for the cluster. The results are insensitive to the choice of alkali atom apart from a smooth trend with the progression from Li to Cs. The calculated total energies suggest that clusters with compositions A₄Pb and A₄Pb₄ are very stable against a change in the number of Pb or A atoms and support the possibility of these clusters forming in the liquid alloys. This stability arises from an electronic shell-closing effect.     

Irradiation-induced defect states in Pb1−xSnxTe under high pressure

Abstract

The galvanomagnetic properties of electron-irradiate n^? and P-Pb_1?x,Sn_xTe (x=O.2) under high hydrostatic Pressure have been investigated. In the irradiated samples the “soft” stabilisation of Fermi level under the irradiation has been revealed and the model of the energy spectrum of irradiated Pb_1?x,Sn_xTe (x=O.2) proposed. The obtained experimental results were used to aetermine the Parameters of radiation-induced resonant band situated slightly below the valence band top.     

ConCm±(n=1-5; m=1,2)团簇的密度泛函理论研究

本文采用基于自旋极化的密度泛函理论系统研究了Co_nC_m^± (n=1-5; m=1,2)团簇的几何结构和电子结构特性. 将Co_nC^± (n=2-5)团簇中的一个Co替换为C原子, 个体的基态几何结构发生明显变化; 在Co_nC₂^± (n=1-5)团簇的生长序列中, 发现从n=3开始团簇中的两个C原子有彼此分离分布的趋势, 我们分析, 这是Co金属能够维持单壁碳纳米管(SCNTs)保持开口生长, 成为非常有效的一种催化剂的重要原因. 同时, 将Co_nC^± (n=2-5)团簇中添加一个Co原子后系统的总磁矩出现大幅下降的趋势, 但仍保持奇偶交替的规律. 通过比较中性及带电的Co_nC以及Co_nC₂ (n=1-5)团簇的碎裂能, 本工作发现: 由实验获取的SCNTs应均为带正电的体系, 这一结论与已有的实验模型拟合得很好.     

幻数尺寸Li-n-1,Lin,Li+ n+1(n=20,40)团簇的几何结构、电子与光学性质的第一性原理研究

基于密度泛函理论,采用第一性原理分子动力学模拟退火方法,对Li^-_n-1,Li_n,Li⁺_n+1 (n=20,40)的最低能量结构进行了全局搜索. 发现锂团簇的生长模式是以单个或多个嵌套的正多面体为核心,其余原子以五角锥为基本单元围绕核心生长. 基于最低能量结构的第一性原理电子结构计算得到锂团簇的分子轨道能级分布与无结构凝胶模型给出的电子壳层完全一致. 在总电 关键词： 团簇 电子结构 极化率 光吸收     

Spatial and electronic structures of the germanium-tantalum clusters TaGe n − (n = 8–17)

The results of optimizing the spatial structure and calculated electronic spectra of the TaGe _n ^? anion clusters (n = 8–17) have been presented. The calculations have been performed in terms of the density functional theory. The most probable spatial structures of clusters detected in the experiment have been determined by comparing the calculated and available experimental data.     

Evolution of structures,stabilities, and electronic properties of anionic [AunRb]− (n = 1–10) clusters: comparison with pure gold clusters

The geometric structures, stabilities, and electronic properties of small size anionic [Au_nRb]^? and Au_n+1^? (n = 1–10) clusters have been systematically investigated by using density functional theory. The optimised geometries show that the structures of [Au_nRb]^? clusters favour the three-dimensional structure at n ≥ 8. The Rb atoms tend to occupy the most highly coordinated position and form the largest probable number of bonds with gold atoms. One Au atom capped on [Au_n-1Rb]^? structures is the dominant growth pattern for n = 2–8 and Rb atom capped on Au_n^? structures for n = 9–10. The averaged atomic bonding energies, fragmentation energies, second-order difference of energies, and highest occupied molecular orbital–lowest unoccupied molecular orbital gaps exhibit a pronounced even–odd alternations phenomenon. The charges in [Au_nRb]^? clusters transfer from the Rb atoms to Au_n host. In addition, it is found that the most favourable dissociation channel of the [Au_nRb]^? clusters is to eject a Rb atom and the highest energy dissociation path is Rb^? anion ejection.     

Ab initio calculation of the geometric,electronic and magnetic properties of neutral and anionic Au n Pd (n = 1–9) clusters

The ab initio method based on density functional theory at the B3PW91 level has been applied to study the geometric, electronic, and magnetic properties of neutral and anionic Au _n Pd (n?=?1–9) clusters. The results show that the most stable geometric structures adopt a three-dimensional structure for neutral Au₇Pd and Au₈Pd clusters, but for anionic clusters, no three-dimensional lowest-energy structures were obtained. The relative stabilities of neutral and anionic Au _n Pd clusters were analysed by means of the dependent relationships between the binding energies per atom, the dissociation energies, the second-order difference of energies, the HOMO–LUMO energy gaps and the cluster size n, and a local odd–even alternation phenomenon was found. Natural population analysis indicates the sequential transfer from the Pd atom to the Au _n frame in Au_1,2,3,5Pd and Au_2,3Pd^? clusters, and from the Au _n frame to the Pd atom in other clusters. Much to our surprise, irrespective of whether it is the total magnetic moment or the local magnetic moment, the magnetic moment presents an odd–even alternation phenomenon as a function of the cluster size n. The magnetic effects are mainly localized on the various atoms (Au or Pd) for different cluster size n.     

Electronic structure and infrared spectrum of a WnC0＇± （n= 1-6） cluster

W_nC^0,± (n=1-6) clusters are investigated by using the density functional theory (DFT) at the B3LYP/LANL2DZ level. We find that the neutral, anionic and cationic ground state structures are similar within the same size, and constituted by substituting a C atom for one W atom in the structures of W_n+1 clusters. The natural bond orbital (NBO) charge analyses indicate that the direction of electron transfer is from the W atom to the 2p orbital of the C atom. In addition, the calculated infrared spectra of the W_nC^0,± (n=2-6) clusters manifest that the vibrational frequencies of neutral, anionic and cationic clusters are similar in a range of 80 cm^-1-864 cm^-1. The high frequency, strong peak modes are found to be an almost stretched deformation of the carbide atom. Finally, the polarizabilities of W_nC^0,± (n=1-6) clusters are also discussed.     

A systematic investigation of the geometries,electronic and magnetic properties of AlnAsq (q = −1, 0, +1; n = 1–16) clusters: a DFT calculation

The geometries, electronic and magnetic properties of Al_nAs^q (q = ?1, 0, +1; n = 1–16) clusters have been investigated systematically by using an unbiased CALYPSO structure searching method and density functional theory. The lowest energy structures show that the As atom prefers to occupy the peripheral position of Al_n+1 clusters instead of the endohedral position. For cationic and neutral clusters, the structural transition from bilayer-like structure to cage-like structure is observed at cluster size n = 12, while it occurs at n = 13 for anionic clusters. The calculated detachment energies (DEs), ionisation potentials (IPs) and electronic affinities (EAs) are consistent with the available experimental and theoretical results for small clusters, indicating that the calculated lowest energy structures are reliable. Furthermore, the DE, EA and IP values for cluster size n ≥ 6 are successfully predicted. A stability analysis shows that Al₅As and Al₁₂As⁺ clusters have relatively large HOMO–LUMO energy gaps, corresponding to the magic numbers of 20 and 40 valence electrons, respectively.     

Structure and stability of small zinc oxide clusters

The structure and stability of small neutral and positively charged zinc oxide (ZnO) _n clusters (n = 2−9) have been studied within the density functional theory. For n ≤ 7, the most stable clusters are shown to be flat rings; for n = 8, 9, the clusters are mainly three-dimensional cage structures. The energies and main channels of fragmentation of the clusters have been determined. It has been found that the fragmentation of the charged clusters with n > 6 occurs predominantly with formation of a (ZnO)₄⁺ ion, which explains the available mass spectrometric data on ionization of the zinc oxide clusters by electron impact.     

Alternation of the spin–orbit coupling in the 2Π ground state of HC n S (n = 1–12) radicals

First-order calculations of spin–orbit constants, dipole moments and carbon–sulphur distances have been performed for HC _n S (n = 1–12) radicals in the ²Π electronic ground state. It is found that these molecular properties alternate with even or odd numbers of carbon atoms in the chains and the spin–orbit constant A _SO is around ?300 cm^?1 for n even and about +120 cm^?1 for n odd throughout the series. This agrees with the experimentally determined value of about ?270 cm^?1 for HC₂S, but the theoretically predicted A _SO values are much larger than the values given for HC₃S and HC₄S from a fit of their millimeter-wave spectra. Values that were too low were also assumed in the analysis of the rotational spectra of n = 4–8.     

Rydberg excitations in rare gas clusters: structure and electronic spectra of Ar* n (3 ≤ n ≤ 25)

Likely candidates are located for the global potential energy minima of Ar* _n (3 ≤ n ≤ 25) clusters using the diatomics-in-molecules (DIM) approach. The favoured geometries are found to be different from the structures of Ar⁺ _n and correspond to the trimer Ar*₃ bound to the surface of an Ar _n?2 core via a common atom. The Ar _n?2 core is usually only slightly distorted from its own global potential minimum, although in a few cases it corresponds to a nearby local minimum. Therefore, the ‘magic’ sizes of the excimer systems are predicted to differ from those of the ions and correlate instead with the stability of Ar _n?2. The predicted electronic photoabsorption and emission spectra of Ar* _n , and photoexcitation spectra of Ar _n are discussed in terms of experimental data. Global potential energy minima for neutral Ar _n up to n = 55 with the Aziz potential are summarized also; the structure is the same as for the Lennard-Jones potential except at n = 21 where the stabilities of the two lowest Lennard-Jones minima are reversed.     

Dopant dependent stability of Co n TM+ (TM = Ti,V, Cr,and Mn) clusters

In this paper, we present a photofragmentation study of mass-selected transition metal-doped cobalt cluster cations Co _n TM⁺  (n = 8–18, TM = Ti, V, Cr, and Mn). Time-of-flight spectra recorded after laser excitation of mass-selected clusters in the gas phase show that the evaporation of a cobalt atom is the most facile dissociation channel for clusters with TM = Ti and V, suggesting an enhanced stability of the doped clusters compared to the bare ones. In contrast, for Co _n TM⁺ with TM = Cr and Mn, the loss of the dopant atom is found to be the preferred dissociation channel. Co₁₃Cr⁺ is a notable exception and favors dissociation by loss of a neutral Co atom. It is implied that substituting Mn and Cr generally destabilizes the cobalt clusters with the exception of Co₁₂Cr⁺, which is relatively more stable than Co ₁₃ ⁺ . Additional measurements of V _n Co⁺ (n = 9–16) show that the loss of a Co atom is still the most facile dissociation channel, which is in agreement with the predicted stronger V?V bond compared to the V?Co one.