Reaction Mechanism of Palladium-Catalyzed Silastannation of Allenes by Density Functional Theory

The reaction mechanism of Pd(O)-catalyzed allenes silastannation reaction is investigated by the density functional method B3LYP. The overall reaction mechanism is examined. For the allene insertion step, the Pd-Si bond is preferred over the Pd-Sn bond. The electronic mechanism of the allene insertion into Pd-Si bond to form sigma-vinylpalladium (terminal-insertion) and sigma-allylpalladium (internal-insertion) insertion products is discussed ill terms of the electron donation and back-donation. It is found that the electron back-donation is significant for both terminal- and internal-insertion. During allene insertion into Pd-Si bond, internal-insertion is preferred over terminal-insertion. By using methylallene, the regio-selectivity for the monosubstituted allene insertion into Pd-Si and Pd-Sn bond is analyzed.

Density functional studies of diatomic LaO to LuO

Bond distances, vibrational frequencies, electron affinities, ionization potentials, dissociation energies and dipole moments of the title molecules in neutral, positively and negatively charged ions were studied by use of density functional method. Ground electronic state was assigned for each molecule. The bonding patterns were analyzed and compared with both the available data and across the series. It was found that besides ionic component, covalent bonds are formed between the metal s, d and f orbitals and oxygen p orbitals. Contrary to the well known lanthanide contraction, the bond distance is not regular from LaO to LuO for both neutral and charged molecules. An obvious population at 5d orbital was observed through the lanthanide series. 4f electrons also participate the chemical bonding for CeO to NdO and TbO to TmO. For EuO, GdO, YbO and LuO, 4f electrons tend to be localized. The spin multiplicity is regular for neutral and charged molecules. The spin multiplicity of the charged molecules can be obtained by -1 (or +1 for TbO+, DyO+, YbO- and YbO+) compared with the corresponding neutral molecules.

A novel approach to synthesis of functional CPVC and CPE or graft copolymers - in situ chlorinating graft

A new process of graft copolymerization of poly(vinyl chloride) (PVC) and polyethylene (PE) with other monomers was developed. The grafted chlorinated poly(vinyl chloride) (CPVC) and chlorinated polyethylene (CPE) were synthesized by in situ chlorinating graft copolymerization (ISCGC) and were characterized. Convincing evidence for grafting and the structure of graft copolymers was obtained using FT-IR, H-1-NMR, gel permeation chromatography (GPC), and the vulcanized curves. Their mechanical properties were also measured. The results show that the products have different molecular structure from those prepared by other conventional graft processes. Their graft chains are short, being highly branched and chlorinated. The graft copolymers have no crosslinking structure. The unique molecular structure will make the materials equipped with special properties.

Revelation of a Functional Dependence of the Sum of Two Uniaxial Strengths/Hardness on Elastic Work/Total Work of Indentation

Dimensional and finite element analyses were used to analyze the relationship between the mechanical properties and instrumented indentation response of materials. Results revealed the existence of a functional dependence of (engineering yield strength sigma(E,y) + engineering tensile strength sigma(E,b))/Oliver & Pharr hardness on the ratio of reversible elastic work to total work obtained from an indentation test. The relationship links up the Oliver & Pharr hardness with the material strengths, although the Oliver & Pharr hardness may deviate from the true hardness when sinking in or piling up occurs. The functional relationship can further be used to estimate the SUM sigma(E,y) + sigma(E,b) according to the data of an instrumented indentation test. The sigma(E,y) + sigma(E,b) value better reflects the strength of a material compared to the hardness value alone. The method was shown to be effective when applied to aluminum alloys. The relationship can further be used to estimate the fatigue limits, which are usually obtained from macroscopic fatigue tests in different modes.

Molecular Dynamics And Density Functional Studies Of A Body-Centered-Tetragonal Polymorph Of Zno

We report a previously unknown body-centered-tetragonal structure for ZnO. This structure results from a phase transformation from wurtzite in [0001]-oriented nanorods during uniaxial tensile loading and is the most stable phase for ZnO when stress is above 7 GPa. The stress-induced phase transformation has important implications for the electronic, piezoelectric, mechanical, and thermal responses of ZnO. The discovery of this polymorph brings about a more complete understanding of the extent and nature of polymorphism in ZnO. A crystalline structure-load triaxiality map is developed to summarize the relationship between structure and loading.

Digitized Processing Track Generation of a Computer Integrated Multi-Functional 5-Axis Laser Processing System

Based on the computer integrated and flexible laser processing system, an intelligent measuring sub-system was developed. A novel model has been built up to compensate the deviations of the main frame-structure, and a new 3-D laser tracker system is applied to adjust the accuracy of the system. To analyze the characteristic of all kind surfaces of automobile outer penal moulds and dies, classification of types of the surface、brim and ridge(or vale) area to be measured and processed has been established, resulting in one of the main processing functions of the laser processing system. According to different type of surfaces, a 2-D adaptive measuring method based on B?zier curve was developed; furthermore a 3-D adaptive measuring method based on Spline curve was also developed. According to the laser materials processing characteristics and data characteristics, necessary methods have been developed to generate processing tracks, they are explained in details. Measuring experiments and laser processing experiments were carried out to testify the above mentioned methods, which have been applied in the computer integrated and flexible laser processing system developed by the Institute of Mechanics, CAS.

Calculations of bond dissociation energies and dipole moments in energetic materials using density-functional methods

We compare the effectiveness of six exchange/correlation functional combinations (Becke/Lee, Yang and Parr; Becke-3/Lee, Yang and Parr; Becke/Perdew-Wang 91; Becke-3/Perdew-Wang 91; Becke/Perdew 86; Becke-3/Perdew 86) for computing C-N, O-O and N-NO2 dissociation energies and dipole moments of five compounds. The studied compounds are hexabydro-1,3,5-trinitro-1,3,5-triazine (RDX), dimethylnitramine, cyanogen, nitromethane and ozone. The Becke-3/Perdew 86 in conjunction with 6-31G