Optimized 3D structures and energy bands of peanut-shaped C60 polymers

Optimized three-dimensional (3D) cell structures and energy bands of fused (peanut-shaped) C₆₀ polymers (p55 and p66) have been investigated using the first-principles pseudopotential approach within the local density approximation of the density functional theory. We found that the resulting electronic structure is either metal or semiconductor depending on the shape of the polymer chains and the unit cell structure.     

Deposition of Ni<Subscript> 13</Subscript> and Cu<Subscript> 13</Subscript> clusters on Ni(111) and Cu(111) surfaces

The soft deposition of Ni₁₃ and Cu₁₃ clusters on Ni(111) and Cu(111) surfaces is studied by means of constant-energy molecular-dynamics simulations. The atomic interactions are described by the Embedded Atom Method. It is shown that the shape of the nickel clusters deposited on Cu(111) surfaces remains rather intact, while the copper clusters impacting on Ni(111) surfaces collapse forming double and triple layered products. Furthermore, it is found that for an impact energy of 0.5 eV/atom the structures of all investigated clusters show the lowest similarity to the original structures, except for the case of nickel clusters deposited on a Cu(111) surface. Finally, it is demonstrated that when cluster and substrate are of different materials, it is possible to control whether the deposition results in largely intact clusters on the substrate or in a spreading of the clusters. This separation into hard and soft clusters can be related to the relative cohesive energy of the crystalline materials.     

The aluminum arsenides Al<Subscript>m</Subscript>As<Subscript>n</Subscript> (m + n = 2–5) and their anions: Structures,electron affinities and vibrational frequencies

Geometries, electronic states and electron affinities of Al_mAs_n and Al_mAs _n (m+n=2–5) clusters have been examined using four hybrid and pure density functional theory (DFT) methods. Structural optimization and frequency analyses are performed using a 6-311+G(2df) one-particle basis set. The geometries are fully optimized with each DFT method independently. The three types of energy separations reported in this work are the adiabatic electron affinity (EA_ad), the vertical electron affinity (EA_vert), and the vertical detachment energy (VDE). The calculation results show that the singlet structures have higher symmetry than that of doublet structures. The best functional for predicting molecular structures was found to be BLYP, while other functionals generally underestimated bond lengths. The largest adiabatic electron affinity, vertical electron affinity and vertical detachment energy, obtained at the 6-311+G(2df)/BP86 level of theory, are 2.20, 2.04 and 2.27 eV (AlAs), 2.13, 1.94 and 2.38 eV (AlAs₂), 2.44, 2.39 and 2.47 eV (Al₂As), 2.09, 1.80 and 2.53 eV (Al₂As₂), 2.01, 1.57 and 2.36 eV (AlAs₃), 2.32, 2.11 and 2.55 eV (Al₂As₃), 2.40, 1.45 and 3.26 eV (AlAs₄), 1.94, 1.90 and 2.07 eV (Al₄As), respectively. However, the BHLYP method gives the largest values for EA_ad and EA_vert of Al₃As and EA_ad of Al₃As₂, respectively. For the vibrational frequencies of the Al_nAs_m series, the B3LYP method produces good predictions with the average error only about 10 cm^-1 from available experimental and theoretical values. The other three functionals overestimate or underestimate the vibrational frequencies, with the worst predictions given by the BHLYP method.     

Silver oligomer and single fullerene electronic properties revealed by a scanning tunnelling microscope

Clusters on surfaces have been investigated with low-temperature scanning tunnelling microscopy and spectroscopy. Constant current spectra acquired on Ag oligomers and one-dimensional chains on a Ag(111) reveal a single resonance peak whose energy shifts towards the Fermi level with increasing cluster size. Next, controlled and reproducible contact between a STM tip and a C₆₀ molecule adsorbed on Cu(100) is reported. The transition from tunnelling to contact is discussed in terms of local heating of the tip-molecule junction.     

Optical and photoelectron spectroscopic studies of alkyl-passivated silicon nanoparticles

We have performed the optical and photoelectron spectroscopic studies of alkyl-passivated Si nanoparticles synthesized by a solution route. The alkyl-passivated Si nanoparticle with mean diameter less than about 2 nm exhibits a strong ultraviolet-blue photoluminescence. Furthermore, we have directly investigated their electronic structures in the vicinity of Fermi level by means of valence-band photoemission measurements using synchrotron radiation. From these results, the detailed optical properties and electronic structures of alkyl-passivated Si nanoparticles are discussed.     

The hydrogenated aluminium trimer: a theoretical examination of the formation and interconversion pathways

Five doublet isomers of the Al₃H₂ cluster lying within a narrow range of 5 kcal/mol, along with the isomerization transition states connecting them, have been located with the coupled-cluster CCSD(T) and DFT methods. The two most stable doublet structures, the C_2v planar including the two Hs bound terminally and C₁ non-planar showing one H in terminal site and the other in threefold site are found to be essentially degenerate. Although the reaction of Al₃ with H₂ to yield Al₃H₂ is found to be significantly exothermic, by 23.5 kcal/mol, this hydrogenation is impeded by a considerable kinetic barrier of 16 kcal/mol. Our result is consistent with the observed lack of reactivity of Al_n towards H₂(D₂) for n=3 under thermal conditions [3]. The quartet Al₃H₂ isomers are predicted to lie 16–21 kcal/mol higher in energy than the doublet analogues. Further dimerization of Al₃H₂ to form Al₆H₄ has also been examined. Electronic supplementary material Supplementary Online Material     

Temperature dependent magnetic spin and orbital moments of mass-filtered cobalt clusters on Au(111)

Mass-filtered cobalt clusters with a size of 8 nm have been deposited in-situ under soft-landing conditions onto Au(111). The spin and orbital moments of the Co nanoparticles on a Au (111) single crystal have been investigated as a function of the temperature using the element-specific method of X-ray magnetic circular dichroism in photoabsorption. The results hint at an temperature-dependent spin-reorientation transition which is discussed with respect to different contribution to the magnetic anisotropy. Furthermore, by means of an in-situ oxidation experiment, the influence of an exposure to oxygen on the properties of the cobalt clusters has been investigated.     

Structural and electronic properties of V, Nb and Ta nanoclusters by tight-binding molecular dynamics simulations

We present tight-binding molecular dynamics (TBMD) calculations on V, Nb and Ta nanoclusters with N = 15, 65, 175 and 369 atoms. We found that rhombic dodecahedra are energetically favoured over rhombic hexahedra and icosahedra, with V forming the most compact cluster with the gyration radius increasing with the cluster size. In addition, from the calculated electronic density of states we found that the cluster size plays an important role in the HOMO-LUMO gap and that an increase in cluster size results in enhancement of the electronic density around the Fermi level. Furthermore, we found that the small clusters (N = 15, 65) exhibit energy gap that persists even at 900 K. These findings originate from charge transfer occurring between the inner and outer cluster atoms; interestingly, we found that in the small N = 15, 65 clusters electronic charge accumulates at each surface site at the expense of the inner cluster atoms, while in the larger clusters, N = 175 and 369, charge is gathered on the central particles of the cluster, suggesting different sub-surface character of the clusters. These findings are in agreement with available experimental and theoretical data and promise to offer important information for creating nanostructured materials with improved properties suitable for multiple technological applications.     

Nanoporous silicon doped by Cu for gas-sensing applications

The effect of hydrogen sulphide on the current–voltage characteristics of metal–insulator–semiconductor (MIS) structures based on nanoporous silicon (Si_nanopor) under copper doping has been investigated. Scanning electron (SEM), atomic force (AFM) and optic microscopes and/or secondary ion mass spectroscopy (SIMS) were used to obtain detailed characterisation of copper cluster distribution present at the surface and pores, respectively. SIMS spectra reveal that finite gradient in copper distribution along the pores and oxidation of nanoporous silicon simultaneously can be obtained successfully under electroless deposition process. It was also shown that the doping of nanoporous silicon by Cu leads to enhanced hydrogen sulphide sensitivity of MIS structures even without catalytic active top electrodes (for example, Pd) at room temperature. Furthermore, for different types of familiar MIS structures based on nanoporous silicon, e.g., MIS structures doped or undoped by copper and by using Pd metal electrodes, the hydrogen sulphide detection at room temperature mainly depends on the modification in the height of barrier of hetero- (Al–Cu–Si_nanopor–c-Si) or Schottky-like (Pd–Cu–Si_nanopor–c-Si) structures resulting the chemical interaction of molecular H₂S gas with copper clusters at the surface and in the pores. It is demonstrated that MIS structures based on the nanoporous silicon with copper doping are more sensitive to H₂S action at room temperature. In addition, the physical mechanism explaining the observed phenomena is also discussed.     

Linear trinuclear Mn-Ln-Mn clusters via the “compartmentalized ligand” approach: Synthesis, structures and magnetic properties

The reaction of a compartmentalized hydrazino Schiff base ligand with a Mn^II salt followed by a Ln^III salt (Ln = Tb and Dy), afforded linear heterometallic MnLnMn complexes that showed interesting magnetic properties.