We present first-principle calculations on symmetric tilt grain boundaries (GBs) in bcc Fe. Using density functional theory (DFT), we studied the structural, electronic and magnetic properties of Σ3(111) and Σ11(332) GBs formed by rotation around the [110] axis. The optimized structures, GB energies and GB excess free volumes are consistent with previous DFT and classical simulation studies. The GB configurations can be interpreted by the structural unit model as given by Nakashima and Takeuchi (2000 ISIJ 86 357). Both the GBs are composed of similar structural units of three- and five-membered rings with different densities at the interface according to the rotation angle. The interface atoms with larger atomic volumes reveal higher magnetic moments than the bulk value, while the interface atoms with shorter bond lengths have reduced magnetic moments in each GB. The charge density and local density of states reveal that the interface bonds with short bond lengths have more covalent nature, where minority-spin electrons play a dominant role as the typical nature of ferromagnetic Fe. In order to understand the structural stability of these GBs, we calculated the local energy and local stress for each atomic region using the scheme of Shiihara et al (2010 Phys. Rev. B 81 075441). In each GB, the interface atoms with larger atomic volumes and enhanced magnetic moments reveal larger local energy increase and tensile stress. The interface atoms constituting more covalent-like bonds with reduced magnetic moments have lower local energy increase, contributing to the stabilization, while compressive stress is generated at these atoms. The relative stability between the two GBs can be understood by the local energies at the structural units. The local energy and local stress analysis is a powerful tool to investigate the structural properties of GBs based on the behavior of valence electrons.

Photoinduced phenomena are of general interest for new materials. Recently, photoinduced molecular desorption of oxygen has been reported in carbon nanotubes. Here we present, using thermopower measurements, that carbon nanotubes when exposed simultaneously to UV light and oxygen exhibit photoinduced oxidation of the nanotubes. At least two plausible mechanisms for the experimentally observed photoinduced oxidation are proposed: (i) a lower energy barrier for the adsorption of photo-generated singlet oxygen, or (ii) due to the presence of defects in carbon nanotubes that may facilitate the formation of locally electron-deficient and electron-rich regions on the nanotubes which facilitate the adsorption of oxygen molecules on the nanotubes.

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We present results of a study of small stoichiometric CdnT en (1≤n≤6) clusters and few medium sized non-stoichiometric CdmT en [(m, n = 13, 16, 19); (m =n)] clusters using the Density Functional formalism and projector augmented wave method within the generalized gradient approximation. Structural properties viz. geometry, bond length, symmetry and electronic properties like HOMO-LUMO gap, binding energy, ionization potential and nature of bonding etc. have been analyzed. Medium sized non-stoichiometric clusters were considered as fragments of the bulk with T d symmetry. It was observed that upon relaxation, the symmetry changes for the Cd-rich clusters whereas the Te-rich clusters retain their symmetry. The Cd-rich clusters develop a HOMO-LUMO gap due to relaxation whereas there is no change in the HOMO-LUMO gap of the Te-rich clusters. Thus, the symmetry of a cluster seems to be an important factor in determining the HOMO-LUMO gap.

Using density-functional theory calculations combined with recent local-energy and local-stress schemes, we studied the effects of Si segregation on the structural, mechanical and magnetic properties of the Σ3(1 1 1) and Σ11(3 3 2) Fe GBs formed by rotation around the [1 1 0] axis. The segregation mechanism was analyzed by the local-energy decomposition of the segregation energy, where the segregation energy is expressed as a sum of the following four terms: the local-energy change of Si atoms from the isolated state in bulk Fe to the GB segregated state, the stabilization of replaced Fe atoms from the GB to the bulk, the local-energy change of neighboring Fe atoms from the pure GB to the segregated GB and the local-energy change of neighboring Fe atoms from the system of an isolated Si atom in the bulk Fe to the pure bulk Fe. The segregation energy and value of each term greatly depends on the segregation site and Si concentration. The segregation at interface Fe sites with higher local energies in the original GB configurations naturally leads to higher segregation-energy gains, while interface sites with lower local energies can lead to larger energy gains if stronger Si-Fe interactions occur locally in the final segregated configurations. The high Si concentration reduces the segregation-energy gain per Si atom due to the local-energy increases of Si atoms neighboring to each other or through the reduction in the number of stabilized Fe atoms per Si atom as observed in a Si dimer in bulk Fe. In the Si-segregated GBs, Si-Fe bonds enhance local Young's moduli and tend to suppress the interface weakening, while the GB adhesion is slightly reduced. And Fe atoms contacting Si atoms have reduced magnetic moments, due to Si-Fe sp-d hybridization interactions.

Starting from ab initio calculations and using a force matching procedure, we have developed a new force field for molecular dynamics simulations of self-assembled monolayers of methylthiolate (MT) on Au(111) surfaces. This new force field is able to reproduce several observed features of SAMs of MT on Au(111) surface, such as the formation of gold vacancy islands and the (√3 × √3)R30 lattice. We have studied the dynamics of Au adatoms and monatomic vacancies on the Au(111) surface for the SAM of MT at room temperature. It is observed that monatomic vacancies coarsen to form large vacancy islands while the adatoms group to form clusters. Both results are in agreement with experiments. At elevated temperatures, Au adatoms that are lifted from the surface leave an atomic vacancy on it. The liquid-like diffusion of gold adatoms on the SAM surface occurs by hopping between pairs of methylthiolate to which the adatom is temporarily bound. Our findings indicate that structural models of the c(4 × 2) unit cell including adatoms and vacancies at room temperature need to be revisited.

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