(KN3)n(n=1~5)团簇结构与性质的密度泛函理论研究

利用密度泛函理论B3LYP方法, 在6-311G*基组水平上对(KN3)n(n=1~5)团簇各种可能的结构进行了几何结构优化, 预测了各团簇的最稳定结构. 并对最稳定结构的振动特性、成键特性、电荷分布和稳定性性质进行了分析研究. 结果表明, 叠氮化合物中叠氮基以直线型存在, KN3团簇最稳定结构为直线型, (KN3)n(n=2~3)团簇最稳定结构为环形结构, (KN3)n(n=4~5)团簇最稳定结构是由(KN3)2团簇最稳定结构形成的平面和空间结构. N-N 键键长在0.1156~0.1196 nm之间, N-K键键长在0.2357~0.2927 nm之间; 叠氮基中间的N原子显示正电性, 两端的N原子显示负电性, 且与K原子直接作用的N原子负电性更强, 金属K原子与N原子之间形成离子键. (KN3)n(n=1~5)团簇最稳定结构的IR光谱最强振动峰均位于2180~2230 cm-1, 振动模式为叠氮基中N-N键的反对称伸缩振动. 稳定性分析显示, (KN3)3团簇具有相对较高的动力学稳定性.     

钠原子团簇的相变

采用紧密结合的分子动力学模型，对Ｎａ４、Ｎａ８、Ｎａ２０的结构特性进行了分析。通过对这些钠原子团簇的键长涨落和径向密度分布的分析，发现在２００Ｋ到２５０Ｋ的温度范围内有从类固相到类液相的改变     

Different self-avoiding walks on percolation clusters: A small-cell real-space renormalization-group study

We calculate the average number of stepsN for edge-to-edge, normal, and indefinitely growing self-avoiding walks (SAWs) on two-dimensional critical percolation clusters, using the real-space renormalization-group approach, with small H cells. Our results are of the formN=AL ^D _SAW+B, whereL is the end-to-end distance. Similarly to several deterministic fractals, the fractal dimensionsD _SAW for these three different kinds of SAWs are found to be equal, and the differences between them appear in the amplitudesA and in the correction termsB. This behavior is atributed to the hierarchical nature of the critical percolation cluster.     

Magnetic properties of the cyclic spincluster Fe6:bicine

The magnetic properties of the cyclic compound [Fe₆(bicine)₆] LiClO₄ ^. 2MeOH are reported. The cluster Fe₆(bicine)₆ forms an antiferromagnetically coupled ring structure of Fe ^III ions. The magnetic susceptibility is measured between 2 and 300 K and yields the exchange coupling of J/k _B = - 27.5±0.5 K. The field dependence of the magnetic moment is studied at 3 and 6 K in magnetic fields up to 5 T. The zero-field splitting of the first excited spin states with S = 2 and 3 are determined by ESR at 94 GHz. The intra-molecular interactions of the Fe ^III ions are analyzed and the on-site anisotropy of the Fe ^III due to the ligand-configuration is determined to d /k _B = - 0.633±0.008K. Received 28 October 2002 / Received in final form 22 February 2003 Published online 20 June 2003 RID="a" ID="a"e-mail: bernd@piobelix.physik.uni-karlsruhe.de     

Interpretive approach to collective effects of electrons in multicenter problems

Interpretive theoretical tools prove valuable in guiding the analysis of experiments in the realm of atomic clusters. Here, we review basic elements of an analytic approach that makes it possible to find and visualize the effective electrostatic potential and Coulomb correlations in multicenter problems. To illustrate the utility of these concepts we apply them to exploring molecular-doped metallic clusters. This study is aiming at a systematic, visual assessment of changes induced in screening, Coulomb correlation and effective potential by varying the charge of the electronegative impurity and its position in the cluster cage.     

Femtosecond pump-probe experiments on non-stoichiometric sodium-fluoride clusters

In this paper we present two-color pump and probe spectroscopy on Na₂F, the smallest of the non-stoichiometric sodium-fluoride clusters (Na_nF_n-1), in molecular beams by employing femtosecond laser pulses. The molecules were pumped into the first excited state by one photonic transition and consecutively ionized from there by the second photon. We resolved the wavepacket oscillatory motion involving periodical structural rearrangements in the first excited state of Na₂F with a period of 185 fs. The time-resolved experiments show that sodium fluoride clusters provide interesting features which can be manipulated in optimal control experiments.     

69,71Ga NMR studies of a superconducting Ga 84 cluster compound

We present ^69,71Ga-NMR experiments on microcrystalline samples of the recently discovered supramolecular compound Ga ₈₄ [ N ( SiMe ₃ ) ₂ ] ₂₀ Li ₆ Br ₂ ( thf ) ₂₀ ^. 2 toluene, which is composed of ligand-coordinated Ga₈₄ metal clusters, packed together in a fully ordered crystalline matrix. The compound is highly conducting and even shows superconductivity below T _c ~ 7.2 K. Our preliminary results between 10-300 K show a metallic-like behavior: the nuclear spin-lattice relaxation rate T ₁ ^-1 follows the Korringa law ⁶⁹ ( T ₁ T ) ^-1 = 0.36 s ^-1 K ^-1 , but with a relaxation rate approximately three times smaller than in bulk -Ga metal. No quantum-size effects are observed, the Korringa law being followed down to 10 K, whereas the quantum-gaps for individual clusters should amount to ~ 10 ³ K. These results therefore suggest a transport process based on intermolecular charge transfer, similar as in alkali-doped fullerenes and silicon-clathrates.     

Kinetics and equilibrium of small metallic clusters: Ab initio confinement molecular dynamics study of 4

The ab initio molecular dynamics (AIMD) [1] is combined with the heuristic, successive confinement method of surveying a potential energy surface (PES) [2], thereby offering a framework for the simulation study of kinetics and equilibrium properties of metallic clusters. This approach is applied to the study of Au₄, a cluster possessing a simple but specific PES, which consists of very shallow and deep basins and due to this presents a challenge to the conventional AIMD methods. Among other things, the probabilities of the transitions between isomers have been found, and on this basis, both the time-dependent and equilibrium populations of the isomers have been calculated for the conditions typical of the NeNePo experiments [3] in the femtosecond pump-probe spectroscopy.     

Thermal and chemical nanofractal relaxation

We studied shape relaxation of nano-fractal islands, during annealing, after their growth from antimony cluster deposition on graphite surface. Annealing at 180^°C shows evidence of an increase of the fractal branch width with time followed by branch fragmentation, without changing the fractal dimension. The time evolution of the width of the arm suggests the surface self-diffusion mechanism as the main relaxation process. With Monte Carlo simulations, we confirmed the observed behavior. Comparison is done with our previous results on fragmentation of nano-fractal silver islands when impurity added to the incident cluster promotes rapid fragmentation by surface self-diffusion enhancement [1].