Initiation of petroleum formation and antioxidant function – a DFT study of sulfur?sulfur bond dissociation enthalpies

Experimental studies showed that sulfur radicals play the vital role in petroleum formation. 1 Sulfur‐ centered radicals also exhibit activities in antioxidant functions. Here we conduct a theoretical investigation of their precursor‐disulfides. By investigation into substituent effect on sulfur? sulfur bond dissociation enthalpies (S? S BDEs), we would like to find the most effective provider for sulfur radicals. In the present work, 50 alpha‐substituted disulfides and 16 para‐substituted aryl disulfides are studied systematically, with the general formula XS‐SX or HS‐SX. The substituent effect on S? S BDEs is found to be very eminent, ranging from 33.2 to 75.0 kcal/mol for alpha‐substituted disulfide, and from 43.7 to 59.7 kcal/mol for para‐substituted phenyl disulfides. We also evaluate the performance of 44 density functional methods to get an accurate prediction. A further study indicates that substituents play a major role in radical energies, instead of molecule energies, which is substantiated by the good linearity between XS‐SX bond dissociation enthalpy (BDE) and HS‐SX BDE. Copyright © 2007 John Wiley & Sons, Ltd.     

腺嘌呤-5-溴尿嘧啶复合物中的卤键

利用从头算和密度泛函理论研究了腺嘌呤(A)-5-溴尿嘧啶复合物中(T+)中的键合模式. 研究结果表明，T+中的Br原子同时与A分子中的氨基氢和氮原子存在弱的相互作用，在这种结合模式中，Br原子与亲核基团H正面结合，同时与亲电基团N侧面结合，分别形成氢键和卤键.静电势分析发现：T+中的Br原子与A中的N7 (或N1)是通过静电相互吸引的. Br与N原子之间的相互作用通过分子中的原子理论得以证实. 关键点的拓扑参数显示卤键是闭壳层相互作用. 自然键轨道分析说明，A中N原子上孤对电子的电荷主要转移到C{Br的反     

Hollow glass microspheres coated with CoFe2O4 and its microwave absorption property

Spinel CoFe₂O₄ coating on the surface of hollow glass microspheres of low density was synthesized by co-precipitation method. The phase structures, morphologies, particle size, shell thickness, chemical compositions of the composites have been characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM) and energy dispersive X-ray spectroscopy (EDS). The results show that CoFe₂O₄ coating on hollow glass microspheres can be achieved, and the coating layers are constituted by CoFe₂O₄ nanoparticles of mean size ca. 10 nm. The as-synthesized powder materials were uniformly dispersed into the phenolic cement, then the mixture was pasted on metal plate with the area of 200 mm×200 mm as the test plate. The test of microwave absorption was carried out by the radar-absorbing materials (RAM) reflectivity far field radar cross-section (RCS) method. The results indicate that the coated CoFe₂O₄/hollow glass microspheres composites can be applied in lightweight and strong absorption microwave absorbers.     

Photoemission studies of initial oxidation for ultra-thin zinc film on 6H-SiC(0 0 0 1) surface with synchrotron radiation

The thermal oxidation process of metallic zinc on 6H-SiC(0 0 0 1) surface has been investigated by using atomic force microscopy (AFM), synchrotron radiation photoelectron spectroscopy (SRPES) and XPS methods. The AFM images characterize the surface morphology of ZnO film formed during the thermal oxidation and SRPES record the valence band, Si 2p and Zn 3d spectra at different stages. The O 1s peak is recorded by XPS because of the energy limit of the synchrotron radiation. Our results reveal that the silicon oxides layer of SiC substrate can be reduce by hot metallic zinc atom deposition. The oxygen atoms in the silicon oxides are captured by the zinc atoms to form ZnO_x at the initial stage and as a result, the oxidized SiC surface are deoxidized. After the zinc deposition with the final thickness of 2.5 nm, the sample is exposed in oxygen atmosphere and annealed at different temperatures. According to the evolution of peaks integrated intensities, it is considered that the Zn/SiC system will lose zinc atoms during the annealing in oxygen flux at high temperature due to the low evaporation temperature of pure zinc. After further annealing in oxygen flux at higher temperature, the substrate is also oxidized and finally the interface becomes a stable SiC-SiO_x-ZnO sandwich structure.     

The effect of Pt on Ni3Al surface oxidation at low-pressures

The fully-oxidized surface that forms on (1 1 1) oriented Ni₃Al single crystals, with and without Pt addition, at 300-900 K under oxygen pressures of ca. 10⁻⁷ Torr was studied using XPS, AES, and LEIS. Two main types of surfaces form, depending upon oxidation temperature. At low-temperature, the predominant oxide is NiO, capped by a thin layer of aluminum oxide, which we refer to generically as Al_xO_y. At high-temperature (i.e., 700-800 K), NiO is replaced by a thick layer of Al_xO_y. By comparing samples that contain 0, 10 and 20 at.% Pt in the bulk, we find that the effect of Pt is to: (1) reduce the maximum amount of both NiO and Al_xO_y; and (2) shift the establishment of the thick Al_xO_y layer to lower temperatures. Platinum also decreases the adsorption probability of oxygen on the clean surface.     

Segregation of Pt at clean surfaces of (Pt, Ni)3Al

Experimental evidence for surface segregation of Pt at (1 1 1) surfaces of ternary (Pt, Ni)₃Al alloys is presented, based upon Auger electron spectroscopy, low energy ion scattering, and angle-resolved X-ray photoelectron spectroscopy. Density functional calculations in the dilute limit confirm that Pt segregation is energetically favored.     

22 dB all-fiber green amplifier using Er-doped fluoride fiber

We demonstrate a 22 dB all-fiber amplifier at 546 nm using Er³⁺-doped fluoride fiber by forward upconversion pumping of a 974 nm laser diode. The gain saturation effects and the power conversion efficiency of this amplifier are investigated in detail based on gain characteristics and numerical simulations.     

Thermochemical process in preparation of ZnO film by TFA-MOD method

The excess weight loss due to the evaporation of zinc compound is observed in the growth of ZnO film by trifluoroacetate metalorganic deposition (TFA-MOD) method. Higher temperature (>90 °C) aging and/or addition of monoethanolamine (MEA) are effective to prevent the evaporation of zinc compound and increase the yield of ZnO. The mechanism of preventing evaporation is that zinc trifluoroacetate is hydrolyzed into Zn₄O(CF₃COO)₆. A three-dimensional structure of Zn₄O(CF₃COO)₆ is proposed. It is shown that higher temperature aging does harm to the surface morphology of ZnO films. The addition of MEA reduces the required aging temperature thus improves the surface morphology.     

Temporal and spectral properties of ultrashort pulsed Laguerre-Gaussian beams in dispersive media

The temporal and spectral properties of ultrashort pulsed Laguerre-Gaussian (LG) beams propagating in dispersive media are studied both theoretically and numerically. It is shown that the on-axis pulse broadens with increasing propagation distance and the on-axis spectrum is blueshifted. For the off-axis spectrum the blueshifts decrease and then the spectrum becomes redshifted as the radial distance increases. The propagation of ultrashort pulsed LG beams in free space and of ultrashort pulsed Gaussian beams can be regarded as special cases of our results, and some interesting properties are discussed.     

Reduction in the electronic band gap of titanium oxide nanotubes

The structural and electronic properties of individual titanium oxide nanotubes have been studied using both empirical and ab initio calculations. Two different types of titanium oxide nanotubes (A-nanotube and B-nanotube) have been constructed and energy-minimized by molecular mechanics calculations. We found that the A-nanotubes are energetically more favorable than the B-nanotubes. The electronic band structure of the titanium oxide nanotubes was also calculated with respect to the tubule diameter and the tubule type using the ab initio method. The band gap of the A-nanotube was reduced by up to 60% as the tubule diameter decreases from 1.2 nm to 0.5 nm.