Size dependent deformation behaviour and dislocation mechanisms in 〈1 0 0〉 Cu nanowires

Abstract

Molecular dynamics simulations have been performed to understand the size-dependent tensile deformation behaviour of 〈1 0 0〉 Cu nanowires at 10 K. The influence of nanowire size has been examined by varying square cross-section width (d) from 0.723 to 43.38 nm using constant length of 21.69 nm. The results indicated that the yielding in all the nanowires occurs through nucleation of partial dislocations. Following yielding, the plastic deformation in small size nanowires occurs mainly by slip of partial dislocations at all strains, while in large size nanowires, slip of extended dislocations has been observed at high strains in addition to slip of partial dislocations. Further, the variations in dislocation density indicated that the nanowires with d > 3.615 nm exhibit dislocation exhaustion at small strains followed by dislocation starvation at high strains. On the other hand, small size nanowires with d < 3.615 nm displayed mainly dislocation starvation at all strains. The average length of dislocations has been found to be same and nearly constant in all the nanowires. Both the Young’s modulus and yield strength exhibited a rapid decrease at small size nanowires followed by gradual decrease to saturation at larger size. The observed linear increase in ductility with size has been correlated with the pre- and post-necking deformation. Finally, dislocation–dislocation interactions leading to the formation of various dislocation locks, the dislocation–stacking fault interactions resulting in the annihilation of stacking faults and the size dependence of dislocation–surface interactions have been discussed.     

Bis(μ‐phenyl 2‐pyridyl ketone N4,N4‐butane‐1,4‐diylthiosemicarbazonato)bis[chlorocopper(II)]

The title compound, [Cu₂(C₁₇H₁₇N₄S)₂Cl₂], exhibits a dimeric structure related by a centre of symmetry. The monomers are linked to each other by the longest Cu—S apical distance observed to date among Cu^II square‐pyramidal complexes of N⁴‐substituted thio­semicarbazones. Each Cu^II atom deviates from the coordination square plane, which contains the pyrid­yl and imine N atoms, the thiol­ate S atom and the Cl⁻ anion, towards the S atom of the adjacent monomer. The dimers pack in a zigzag manner through the crystal.     

The determination of organochlorine pesticides and polychlorinated biphenyls by combustion tube decomposition and molecular emission cavity analysis

The determination of microgram quantities of chlorine in polychlorinated biphenyls and organochlorine insecticides by molecular emission cavity analysis is described. Samples either pure, in admixture or mixed with sand were decomposed at 900 ± 50°C in a quartz combustion tube in a humidified oxygen atmosphere. The products of decomposition were bubbled through water or 1% ammonia and 4-μl aliquots of the solution obtained were injected into a stainless steel indium-lined cavity and heated in a nitrogen/hydrogen flame. The chlorine was quantified by comparing the intensity of the InCl emission at 360 nm with that obtained from hydrochloric acid standards. The effect of potential interferences such as alkali and alkaline earth metals, nitrogen, phosphorus, sulphur, carbon aluminium and iron were studied. Except for the alkali and alkaline earth elements, the recoveries of the compounds burned were not affected. Where the elements interfered, methods for eliminating the interferences are described. The chlorine recovery was usually >90%.     

Novel 36-membered dodecanuclear manganese metalladiazamacrocycle

A novel dodecanuclear manganese metalladiazamacrocycle was synthesized employing a new pentadentate ligand N-2-pentenoylsalicylhydrazide (H(3)tpeshz) by supramolecular self-assembly. The backbone of this metal-organic assembly is a repeating unit of an M-N-N-M linkage that extends to complete a 36-membered cyclic structure involving 12 manganese(III) centers. Successive manganese centers are in a chemically different ...ABABAB...-type environment while the chirality varies as ...LambdaLambdaDeltaDeltaLambdaLambda... . The unique arrangement of manganese centers results in a highly puckered metalladiazamacrocycle with an S(6)-point group symmetry.     

Porous metal-organic frameworks based on metal-organic polyhedra with nanosized cavities as supramolecular building blocks: two-fold interpenetrating primitive cubic networks of [Cu6L8]12+ nanocages

Discrete metal-organic polyhedra (MOP) with nanosized cavities and/or clusters of MOP could be prepared when C3-symmetric facial ligands and a potential hexatopic Cu(II) ion are combined in the presence of perchlorate as a weak linker, while similar reaction conditions in the presence of a nitrate linker led to extended metal-organic frameworks made of MOP as supramolecular building blocks.     

Face-driven corner-linked octahedral nanocages: M6L8 cages formed by C3-symmetric triangular facial ligands linked via C4-symmetric square tetratopic Pd(II) ions at truncated octahedron corners

The face-driven corner-linked truncated octahedral nanocages, [Pd6L8]12+ (1, L1 = N,N',N' '-tris(3-pyridinyl)-1,3,5-benzenetricarboxamide; 2, L2 = N,N',N' '-tris(4-pyridinylmethyl)-1,3,5-benzenetricarboxamide), were prepared with eight C3-symmetric tridentate ligands and six square planar tetratopic palladium(II) ions. The combination of the nitrogen donor atom at a approximately 120 degrees kink position of the carboxamido pyridinyl group and the tilted pyridyl versus the facial plane of the ligands can provide the needed curvature for the formation of octahedral cages. The nitrogen atoms can coordinate to the square planar palladium(II) ions to form kinks with approximately 120 degrees angles at the C4-symmetric square planar corners of the truncated octahedron. Depending on the conformation of the ligand, L1, two different truncated octahedral cages of around 2.4 nm in diameters were formed. The major form of 1 with syn-conformational ligands has a cavity volume of approximately 1600 A3. The cage has 12 ports (3.4 x 3.5 A2) at all edges of the octahedron. The minor form of cage 1 with anti-conformational ligands has a slightly increased cavity volume ( approximately 1900 A3) and port size (3.3 x 8.0 A2). The insertion of a methylene group in L2 has not only increased the cavity volume of 2 to approximately 2200 A3 but also enlarged the port size to 4.1 x 8.0 A2. However, an atomic force microscopy (AFM) study of cage 2 showed that the cages had a height of 1.8 +/- 0.1 nm. This value is about 30% smaller than the calculated size of 2.6 nm from the crystal structure. This tip-induced decrease in height in cage 2 suggests the nonrigidity of cage 2.     

Synthesis,spectral characterization and crystal structure of copper(II) complexes of 2-hydroxyacetophenone-N(4)-phenyl semicarbazone

Six new copper(II) complexes of 2-hydroxyacetophenone-N(4)-phenyl semicarbazone have been synthesized and physico-chemically characterized. The tridentate character of the semicarbazone is inferred from IR spectra. Based on EPR studies, the spin Hamiltonian and bonding parameters have been calculated. The g   values, calculated for all the complexes in frozen DMF, indicate the presence of the unpaired electron in the d_x2-y2${\text{d}}_{x^2-y^2}$ orbital. The metal–ligand bonding parameters evaluated showed strong in-plane σ and in-plane π-bonding. The structure of the compound, CuLphen has been resolved using single crystal X-ray diffraction studies. The crystal structure revealed a monoclinic lattice with space group symmetry P2₁/c. The compound adopts a distorted square pyramidal geometry with a N₂O₂ core as the base.     

Two octanuclear gallium metallamacrocycles of topologically different connectivities

Two topologically different metallamacrocycles--S8 symmetric octanuclear gallium(III) metalladiazamacrocycle and pseudo-D4 symmetric octanuclear gallium(III) metalladiazamacrocycle--could be prepared using two similar heteroditopic bridging ligands having asymmetrical tridentate-bidentate binding residues.