Electronic and geometric structure of doped rare-gas clusters: surface, site and size effects studied with luminescence spectroscopy

The electronic and geometric structure of rare gas clusters doped with rare-gas atoms Rg = Xe, Kr or Ar is investigated with fluorescence excitation spectroscopy in the VUV spectral range. Several absorption bands are observed in the region of the first electronic excitations of the impurity atoms, which are related to the lowest spin-orbit split atomic ³P₁ and ¹P₁ states. Due to influence of surrounding atoms of the cluster, the atomic lines are shifted to the blue and broadened (“electronical cage effect”). From the known interaction potentials and the measured spectral shifts the coordination of the impurity atom in Ar_N, Kr_N, Ne_N and He_N could be studied in great detail. In the interior of Kr_N and Ar_N the Xe atoms are located in substitutional sites with 12 nearest neighbours and internuclear distances comparable to that of the host matrix. In Ne_N and He_N the cluster atoms (18 and 22, respectively) arrange themselves around the Xe impurity with a bondlength comparable to that of the heteronuclear dimer. The results confirm that He clusters are liquid while Ne clusters are solid for N≥ 300. Smaller Ne clusters exhibit a liquid like behaviour. When doping is strong, small Rg_m-clusters (Rg = Xe, Kr, Ar, m≤10 ²) are formed in the interior sites of the host cluster made of Ne or He. Specific electronically excited states, assigned to interface excitons are observed. Their absorption bands appear and shift towards lower energy when the cluster size m increases, according to the Frenkel exciton model. The characteristic bulk excitons appear in the spectra, only when the cluster radius exceeds the penetration depth of the interface exciton, which can be considerably larger than that in free Rg_m clusters. This effect is sensitive to electron affinities of the guest and the host cluster.     

Electronic structure of Al clusters containing 3 d impurity atoms: Fe, Co, and Ni

The size dependence of the electronic structure of Al clusters containing 3d impurity atoms, Fe, Co and Ni, has been self-consistently calculated within the model of an atom built-in in a spherical jellium cluster and the local-density functional theory. It is found that the electronic structure of Al jellium clusters containing an impurity 3d atom at the center periodically changes with an increase in cluster size.     

BmPn和BmP-n(m+n≤5)团簇的几何结构与稳定性

采用密度泛函理论(DFT)的B3LYP方法,在6-31G(d)水平上对BmPn(m n≤5)团簇及其阴离子的几何构型、电子结构和振动光谱等性质进行了理论研究.并在相同水平下计算了BmP-n(m n≤5)的垂直电离能和BmPn(m n≤5)的绝热电子亲和势.结果表明:BP、B2P2、B3P2、B4P较稳定,而BP2、BP3、B2P3、BP4的稳定性较差;B2P-较容易失去一个电子形成B2P,B3P-和B2P-3的垂直电离能力基本相同.     

Electronic structure and dynamics of ordered clusters with ME or RE ions on oxide surface

Selected data of ab initio simulation of the electronic structure and spectral properties of either cluster with ions of iron, rare earth or actinium group elements have been presented here. Appearance of doped Cr⁺⁴ ions in oxides, Cu⁺² in HTSC, Nd⁺² in solids has been discussed. Analysis of experimental data for plasma created ordered structures of crystallites with size of about 10^-9 m on surface of separate oxides are given, too. Change in the spectroscopic properties of clusters and nano-structures on surface of strontium titanate crystals discussed shortly using the X-ray line spectroscopy experimental results.     

Electronic structure of carbon nanotubes modified by alkali metal atoms

The electronic structure and parameters of the energy band structure of (n, 0)-type nanotubes modified by alkali metal atoms (Li, Na) and intercalated by potassium atoms are studied. The quantum-chemical semiempirical MNDO method and a model of the covalent cyclic cluster built in via ionic bonding are used to model infinitely long nanotubes. The electronic density of states of modified nanotubes is found. It is shown that semiconductor-metal transitions can occur in semiconductor nanotubes and that semimetal nanotubes can undergo metal-metal transitions.     

Collisional broadening and shift of Doppler-free two-photon thallium lines perturbed by rare-gas atoms

The extended Omont-Ueda-Kaulakys treatment of collisional effects on quasi-Rydberg states, in which the perturbation of the lower state is taken into account is applied to thallium-rare gas systems. The pressure broadening and shift coefficients of two-photon transitions in thallium involving the 6P_1/2 -n P_1/2,3/2 (n = 9-14) states are calculated and compared with experimental data obtained by Hermann et al. [Eur. Phys. J. D 1, 129 (1998)].     

Electronic structure, energetics and geometric structure of carbon nanotubes: A density-functional study

Based on the local density approximation (LDA) in the framework of the density-functional theory, we study the details of electronic structure, energetics and geometric structure of the chiral carbon nanotubes. For the electronic structure, we study all the chiral nanotubes with the diameters between 0.8 and 2.0 nm (154 nanotubes). This LDA result should give the important database to be compared with the experimental studies in the future. We plot the peak-to-peak energy separations of the density of states (DOS) as a function of the nanotube diameter (D). For the semiconducting nanotubes, we find the peak-to-peak separations can be classified into two types according to the chirality. This chirality dependence of the LDA result is opposite to that of the simple π tight-binding result. We also perform the geometry optimization of chiral carbon nanotubes with different chiral-angle series. From the total energy as a function of D, it is found that chiral nanotubes are less stable than zigzag nanotubes. We also find that the distribution of bond lengths depends on the chirality.     

Electronic structure of MgO-supported Au clusters: quantum dots probed by scanning tunneling microscopy

We investigate via density functional theory (DFT) the appearance of small MgO-supported gold clusters with 8 to 20 atoms in a scanning tunneling microscope (STM) experiment. Comparison of simulations of ultrathin films on a metal support with a bulk MgO leads to similar results for the cluster properties relevant for STM. Simulated STM pictures show the delocalized states of the cluster rather than the atomic structure. This finding is due to the presence of s- derived delocalized states of the cluster near the Fermi energy. The properties of theses states can be understood from a jellium model for monovalent gold.     

The hyperfine structure of heavy hydrogen-like ions: Calculation based on experimental data on muonic atoms

A procedure for the calculation of the correction to the hyperfine structure of hydrogen-like ions for the Bohr-Weisskopf effect is developed on the basis of experimental data on muonic atoms. The calculations take into account the quantum electrodynamic corrections both for muonic atoms and for electronic ions. The single-particle model and the configuration mixing model of the nucleus are considered. The results of the calculations are compared with known theoretical and experimental data.     

Static polarizabilities of helium and alkali atoms,and their isoelectronic ions

A rather simple method of calculation of the scalar and tensor components of static polarizability was developed for a wide range of atoms and ions. The general formulas for polarizabilities of SL terms, J levels, and F components of hyperfine structure are given. The results of calculation for ground and some excited states of He and alkali atoms (Li, Na, K, Rb, Cs) are presented. The comparison of the results with available theoretical and experimental data shows that, in most cases, the differences do not exceed 10%. The polarizabilities for the Li+, Be+, B²+, C³+, Ne⁷+, Mg+, Al²+, Si³+, Ar⁷+, Ca⁺, Sc²+, Ti³+, Sr⁺, and Ba⁺ ions are also given.